Mono-and disazo dyestuffs containing triazinylureylene groups

ABSTRACT

Reactive dyestuffs of the formula   R is a member selected from the group consisting of H and lower alkyl; D is an azo dyestuff chromophoric radical Hal is F, C1, or Br; N IS ONE OF THE INTEGERS 1 OR 2; AND X is a monovalent electron-donnor substituent, selected from the group of lower alkoxy, phenoxy, halogen-substituted phenoxy, lower alkyl-substituted phenoxy, lower alkoxy-substituted phenoxy, lower alkylthio, phenylthio, halogen-substituted phenylthio, lower alkyl-substituted phenylthio, lower alkoxysubstituted phenylthio, lower alkylamino, di(lower)alkylamino, phenylamino, N-lower alkyl-N-phenylamino, N-lower alkyl-Nhalogen-phenylamino, N-lower alkyl-N-lower alkylphenylamino, Nlower alkyl-N-lower alkoxyphenylamino, piperidino or morpholino, halogen being chloro or bromo. These dyes are suitable for the dyeing of natural and synthetic polyamide fibers as well as for textile fibers containing hydroxyl groups, particularly for natural or regenerated cellulose fibers. The obtained dyeings and prints are distinguished by excellent wet fastness properties and good fastness to light.

United States Patent [72] Inventors Hans Aekermann;

Herbert S'eiler; Hubert Melndl, all of Riehen, Switzerland [21] Appl. No. 800,300 [22] Filed Nov. 8, 1968 [45] Patented Dec. 14, 1971 [73] Assignee J. R. Geigy A.G.

Basel, Switzerland [32] Priorities July 10, 1963 [3 3 Switzerland [31] 8591/63;

Aug. 19, 1963, Switzerland, No. 10134/63; Jan. 8, 1965, Switzerland, No. 265/65 Continuation of application Ser. No. 517,998, Jan. 3, 1966, now abandoned and a continuation-in-part of 380,677, July 7, 1964, now abandoned. This application Nov. 8, 1968, Ser. No. 800,300

[54] MONO-AND DISAZO DYESTUFFS CONTAINING TRIAZINYLUREYLENE GROUPS 6 Claims, No Drawings [52] US. Cl 260/153, 8/4, 8/41, 8/42, 8/43, 8/50, 8/51, 8/71,117/138.8, 260/37, 260/141, 260/146, 260/147, 260/148, 260/149, 260/151, 260/163, 260/186, 260/191, 260/196, 260/199, 260/242, 260/249, 260/2498, 260/314.5, 260/372, 260/374 [51] Int. Cl 09 62/ C09b 62/06, C09b 62/08 F 50] Field of Search 260/146, 153,147, 242, 249, 249.5, 249.8

[56] References Cited 7 UNITED STATES PATENTS 3,110,710 11/1963 Ratleeetal 260/153 3,116,275 l2/1963 Gamleu et al.... 2 6Q /1 5 3 K OTHER REFERENCES Venkataraman, The Chemistry of Synthetic Dyes, Volume 1, Ch. 5, pp. 240-247, Academic Press lnc., Publishers, New York 1952).

Primary Examiner- Floyd D. l-ligel Attorney-Wenderoth, Lind & Ponack ABS'ljRCT: Reactive dyestuffs of the formula H993?! w M M R -I I- is connected to a ring carbon of D;

R is a member selected from the group consisting of H and lower alkyl;

D is an azo dyestuff chromophoric radical Hal is F,C1,orBr; n is one of the integers l or 2; and X is a monovalent electron-donnor substituent, selected from the group of lower alkoxy, phenoxy, halogen-substituted MONO-AND DISAZO DYESTUFFS CONTAINING TRIAZINYLUREYLENE GROUPS This application is a continuation of application Ser. No. 517,998, filed Jan. 3, 1966, abandoned since the filing of the instant application, which application is in turn a continuation-in-part of application Ser. No. 380,677, filed July 6, 1964, now abandoned.

The present invention relates to reactive dyestuffs, processes for the production thereof, their use for the dyeing of organic textile fibers containing hydroxyl and/or amino groups, as well as, as industrial product, the fiber materials dyed with the aid of these dyestuffs.

It has been found that dyestuffs which, surprisingly can be fixed onto textile fibers containing hydroxyl and amino groups and afford dyeings of good fastness properties, are obtained by reaction one mol of an organic dyestuff of the formula wherein D represents the radical of an organic dyestuff, capable of withstanding the conventional conditions of dyeing textile fibers containing in their molecule hydroxyl and/or amino groups with fiber-reactive dyestuffs, and subsequent fixation by thermofixing or steaming,

R represents hydrogen or lower alkyl, and

n represents 1 or 2, with n mol of a compound capable of yielding the radical of the formula II I N (lower alkyl) wherein Hal represents halogen of one of the atomic numbers 9, 17,

or 35, i.e., fluorine, chlorine or bromine,

X represents a monovalent electron-donating substituent containing a hetero atom of one of the atomic numbers 7, 8, and 16, by way of which atom said substituent is linked to the triazinyl ring in formula ll, and the molecular weight of which substituent does not exceed 200,

to form a dyestuff of the formula N N (lower alkyl) wherein D, R, and n have the same meanings as in formula I, and

Hal and X have the same meanings as in formula ll, or by forming the reactive dyestuffs of formula III from components of which at least one contains the radical of formula ll bound by way of an amino group of the formula and treatment, at least during subsequent thermofixation or steaming at elevated temperatures of about to C. in a strongly alkaline medium, but that the triazinyl lower alkylamino radical would be split from the CO--NR bridge of formula III during dyeing, so that no fixation of the dyestuffs to the fiber molecule could take place.

Indeed, this would occur if X in formula III would represent an electron-accepting substituent. Furthermore, intermediates with such a substituent would not be readily available.

It is one surprising feature of the dyestuffs according to the invention that the bond of the triazinyl radical to the urea bridge in the dyestuffs of formula III, in which X has the above-defined meaning, and via the urea bridge to the dyestuff-character imparting principal moiety of the molecule in formula III is so strong that the severe conditions of reactive dyeing, especially on cotton but also on wool or nylon, are withstood without substantial decomposition, and that commercially useful dyeings of satisfactory fastness properties are obtained.

The reaction between the fiber molecule and the reactive dyes falling under formula III takes place substantially entirely by splitting off the Hal substituent from the triazinyl reactive group.

In formulas l and III, D represents in particular the radical of, for example, a mono-, dis-, or polyazo dyestuff which may contain heavy metal in complex bond, an anthraquinone, a nitro or a phthalocyanine dyestuff.

In those compounds of formula III in which D represents the radical of an azo dyestuff, it is, for example, the radical of a monoazo dyestuff of the benzene-azo-benzene, benzene-a20- naphthalene, benzene-azo-pyrazole, benzene-azo-acetoacetylarylamide, naphthalene-azo-naphthalene and naphthaleneazo-pyrazole series, or the radical of a disazo dyestuff of the benzene-azo-benzene-azo-benzene, benzene-azonaphthalene-azo-benzene and naphthalene-azo-benzene-azobenzene series, all of which may be free from or may contain heavy metal in complex bond, or of a metal-containing formazane dyestuff.

In those compounds of formula III in which D is the radical of an anthraquinone dyestuff, it is preferably a l-amino-4 phenylaminoor l-amino-4-diphenylamino-anthraquinone radical.

When D is the radical of a phthalocyanine dyestuff, it is preferably the radical of phthalocyanine sulfonic acid alkylamide or arylamide, which preferably contains sulfonic acid groups.

The organic dyestuffs of formula I contain the groups either in the internal, principal dyestuff structure or at an external substituent, such as at the benzene ring of benzoylamino or of phenyl-amino groups.

The dyestuffs mentioned can contain shade and fastness properties-influencing substituents.

Such shade and fastness properties-influencing" types of substitution in the dyestuffs according to the invention are: fluorine, chlorine, bromine, lower alkyl groups having straight or branched chains such as the methyl, ethyl, propyl, isopropyl, n-butyl, tert. butyl and amyl group, cycloalkyl groups such as the cyclohexyl and the methyl-cyclohexyl group, aralkyl groups such as the benzyl or phenethyl group, other groups such as lower alkoxy, e.g., methoxy, ethoxy, or benzyloxy or phenoxy group, lower alkyl-sulfonyl, carboxylic acid and sulfonic acid groups, acylamino groups such as the acetylamino, chloroacetylamino, B-bromopropionylamino, phenylamino and benzoylamino group, carboxylic acid amide and sulfonic acid amide groups which may be N-substituted, also the nitro, amino, carbamido, amino-phenyl-SO NH S0 and hydroxyl groups.

R, when representing a lower alkyl group is, for example, the methyl or ethyl group; preferably, however, it represents hydrogen.

The reactivity of dyestufis of formula III according to the invention in which Hal is fluorine is superior to that of dyestuffs in which Hal is chlorine. They can thus be fixed onto the fiber at relatively low temperatures, whereas dyestuffs in which Hal is chlorine require higher fixing temperatures or stronger bases, e.g., sodium hydroxide, as acid-binding agents.

The lower alkyl substituent at the nitrogen atom in formula III to which the triazinyl radical is attached is, for example, methyl, ethyl, isopropyl or butyl.

The monovalent electron-donating substituent X which is of a molecular weight not exceeding 200, and preferably below 150, represents, for example, ether groups such as an alkoxy group, e.g., the methoxy or the ethoxy group; an aryloxy group, in particular the unsubstituted phenoxy group, but also a phenoxy group substituted by halogen, e.g., chlorine, by lower alkyl or lower alkoxy; a thioether group, in particular a lower alkylthio group such as the methylthio group or ethylthio group as well as an arylthio group, in particular the unsubstituted phenylthio group or a phenylthio group substituted by halogen, e.g., chlorine, by lower alkyl or lower alkoxy. Especially, however, X represents an amino group derived from a primary or secondary organic, preferably aliphatic amine, in particular a monoalkylamino or dialkylamino group such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert, butylamino, dimethylamino, diethylamino, dipropylamino or dibutylamino.

The lower monoand dialkylamino radicals are preferred on account of the higher solubility of the resulting reactive dyestuffs of formula III.

In starting materials containing the grouping of formula II, the lower dialkylamino radicals are preferred because of the more uniform phosgenization in the synthesis of these starting materials. Furthermore, the radical X may be derived from saturated heterocyclic nitrogen bases such as piperidine or morpholine; or X may represent the radical of a phenylamino or Nlower-alkylN-phenylamino group the phenyl radical of which is unsubstituted or substituted by halogen, e.g., chlorine or bromine, or by lower alkyl or lower alkoxy.

Amino dyestuffs of formula I, into the molecules of which the fiber-reactive grouping according to the invention can be introduced are, for example, amino-anthraquinones such as lamino-4-(mor p-amino-phenylamino)- or 4-(o-, or m'- or p'-amino-diphenylamino)-anthraquinones and their sulfonic acids; aminophthalo-cyanines such as condensation products of phthalocyanine sulfonic acid chloride with alkylenediamines or with arylene-diamines which may be sulfonated; and also aminoazo dyestuffs as well as the sulfonic acids thereof. The latter contain acylatable amino groups in the coupling component and/or in the diazo component.

For instance, aminoazo dyestuffs of the formula are particularly valuable starting materials. In this formula A represents the radical of a diazo component, particularly a benzene diphenyl or naphthalene radical which is unsubstituted or bears a shade and fastness properties-influencing substitution of the type further described hereinbefore, B represents the radical of a coupling component, R and n have the same meanings as in fonnula l. Preferably A and B together contain at least two sulfonic acid groups.

The azo dyestuffs of formula IV are obtained, for example, by coupling optionally sulfonated acylamino-phenyl, acylaminodiphenyl or acylaminonaphthyl diazonium compounds or nitroaryldiazonium compounds, more particularly, for example, by coupling a diazotized acetyl-amino aniline 4- acetylamino-4-amino-l,l-diphenyl or a nitroaniline which may contain sulfonic acid groups, with conventional coupling components, e.g., with those of the benzene, naphthalene, pyrazole or acyloacetyl-arylamide series, then saponifying the acylamino group or reducing the nitro group to the amino group. They are also obtained by coupling a diazonium compound with a coupling component containing acylatable amino groups, e.g., with an aminobenzene, aminonaphthalene or aminonaphthol, or also with an aminoaryl pyrazolone or aminoaryl pyrazole imine or with an acyloacetylarylamide or with their sulfonic acids.

Other valuable starting materials are metal-containing aminoazo dyestuffs of the formula wherein A represents a benzene or naphthalene radical which is unsubstituted or bears a shade and fastness properties-influencing substitution, as described hereinbefore,

B represents the radical of a coupling component,

Me represents a heavy metal of the atomic numbers 24 to 29 which can also contain other coordinated complex formers,

Y represents oxygen or the COOgroup, and

R and n have the same meanings as in formula I.

The bridge members Y and the oxygen atom in formula V are linked to A and B, respectively, in orthoposition to the azo bridge, N= N-.

Preferably, the aminoazo dyestuffs of formula V contain at least two sulfonic acid groups.

Metallized aminoazo dyestuffs of this type are obtained, for example, by coupling optionally sulfonated acylamino-phenyl or acylamino-naphthyl or nitro-phenyl diazonium compounds which preferably contain a hydroxyl, alkoxy or carboxyl group in the o-positioned to the diazonium group, with conventional coupling components capable of coupling in a position adjacent to a hydroxyl group, e.g., phenols, naphthols, pyrazolones, or acyloacetylarylamides, and also the sulfonic acids of these compounds. They are also obtained by coupling the usual aromatic diazonium compounds, particularly optionally sulfonate o-hydroxyaryl, o-alkoxyaryl or o-carboxyaryl diazonium compounds with coupling components capable of coupling in "a position adjacent to a hydroxyl group, which coupling components may contain an acylated amino group, e.g., with an aminonaphthol or acylaminonaphthol, or with an aminonaphthol or acylaminonaphthol sulfonic acid. After the acylamino group has been hydrolyzed or the nitro group has been reduced to the amino group, the aminoazo compounds obtained are converted into heavy metal complexes with agents yielding chromium, cobalt, nickel, or copper, if necessary in the presence of an oxidizing agent. To saturate any other coordination positions present, the dyestuffs according to the invention can also contain other complex-forming compounds which may have dyestuff character and are bound by way of the heavy metal, for example, water, certain tertiary amines such as pyridine or another o,o'-dihydroxyor o-hydroxy-o'- carboxyazo dyestuff.

Compounds usable according to the invention which introduce the radical of formula ll, above, into the dyestuff starting materials of formula I are mainly the carbamic acid chlorides of the formula llalC Diazonium compounds of formula VIII used in this process are derived from optionally sulfonated aryI-enediamines, such as por m-phenylenediamine suifonic acid or 2,6- naphthylene-diamine-4,8-disulfonic acid.

wherein Hal and X have the same meanings as in formula II.

The carbamic acid chlorides of formula VI are obtained by known processes, in particular by reacting halogen-amino-striazines compounds of the formula N filower alkyl) tional in azo dyestuffs, for example, those of the benzene sei ries such as phenols or anilines, of the naphthalene series such W N as optionally sulfonated naphthols, naphthylamines or phenyl- N and acyl-aminonaphthols, furthermore, pyrazolones, pyrazole j 10 imines or acyloacetylarylamides.

l A further method of performing the process for the production of reactive dyestuffs of fonnula III comprises reacting an aryl diazonium compound (AN,) (anion)' with a coupling component of the formula hydrocarbons such as toluene, chlorobenzcne or R nitrobenzene. l O

The reaction of an amino dyestuff of formula I with the acylating agent introducing the radical of formula II, III-(lower alkyl) preferably a compound of formula VI, is advantageously performed in aqueous solution, optionally in the presence of inert organic solvents, e.g., lower alkanols, lower aliphatic ketones I l or lower fatty acid amides, if necessary in the presence of I-Ial N X Components to be coupled therewith are those conven buffer salts or tertiary nitrogen bases such as dialkyl anilines as "M 9 acid binding agents. To prevent a premature exchange of substituents which can be split off, the reaction is perfonned with care under mild conditions, preferably at a pH of 4 to 8 and at as low temperatures as possible. Mild conditions are also indicated for the isolation and drying of the reaction products.

Reactive dyestufis of formula III are also obtained by a modified process by forming them from dyestuff components! wherein R has the same meaning as in formula I,

Hal and X have those given in formula II and B represents the radical of an azo dyestuff forming coupling component, to produce a dyestuff of the formula R which contain at least one radical of formula II bound by way I of an amino group A1 -N=NBNC 0 N(lower alkyl) I\ I R v N/ \N This method is particularly suitable for the production of azo I H dyestuffs and comprises coupling an aromatic diazonium coma (XI) pound with a coupling component, at least one of which conwherein tains the characteristic fiber-reactive acylamino group accord- B Hal R and X have he same meanings as in fonnula X ing to the invention.

For example, a diazonium compound of the formula l in the diam component represenw a radb cal of the benzene, diphenyl, naphthalene or azo dyestnif N s c n i series which may be further substituted, and, if desired, Haklo fi" N CO N A"Ni converting a dyestuff thus obtained which possesses N /N (lower alkyl) metaliizable substituents in A, and B, to a heavy metal complex thereof, with agents giving off heavy metal.

I Diazotized aromatic amines usual in azo dyestuffs are used X (VH1) in this process as diazonium compounds, for example, op-

wherein tionally sulfonatcd phenyl, diphenyl, naphthyi or azo dyestuff A. represents a nzen ph nyl o n ph h lene r i l r diazonium compounds. The latter are especially benzene-azoan 810 y m l, which m y have furl-her "Shade benzene-diazonium, benzene-azo-naphthalenediazonium, or and fastness properties-influencing" substitu 8S naphthalene-azo-benzene-diazonium compounds.

described hereinbcfore, In formula X, B, the radical of the coupling component of R has thc same meaning as in formula and the dyestuff of formula XI, represents, for example, the radical Hal and x have the same meanings as in formula of an aminonaphthol sulfonic acid such as the radical of a lis mupled with a P 8 compmlem to form azo amino-6- or -7 hydrox y-naphthalene sulfonic acid, of ldyestuffof the fm'mula amino-8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid, of 2- amino-8-hydroxynaphthalene-6-sulfonic acid or of 2-amino-5- f 55 hydroxynaphthalene-7-sulfonic acid, or the radical of an op- HaPC tionally sulfonated aminoaryl pyrazolone or pyrazole imine or N (lower alkyl) of an acyIacetyI-arylamide.

C Azo dyestuffs containing two radicals of formula II are obtained, for example, by coupling a diazonium compound of r X was. Q29 formula VIII with acoupling component of formula X.

The coupling is performed in every case in a weakly acid to weakly alkaline medium by the visual methods.

wherein A, has the same meaning a: In fonnula VIII, and

8 represents the radical of a coupling component; if desired, metaiiinblc dyestuffs thus obtained are then reacted with agents introducing a complex-forming heavy metal.

Both the coupling and the metallization must be performed under mild conditions, i.e., high pH values and temperatures should be avoided.

The dyestuffs obtained can be stabilized with buffer substances, for example with mixtures of primary and secondary alkali phosphates or with alkali metal salts of sulfonated tertiary aromatic amines, that is, for example, with the sodium salt of N,N-dimethylaniline-Zi-sulfonic acid.

The preferred dyestuffs of formula ill contain water-solubilizing, salt-forming groups and are suitable for the dyeing of natural and synthetic polyarnide fibers containing amino groups. An aftertreatrnent of the dyeing with acid-binding agents such as ammonia or hexamethylenetetramine improves the wet fastness properties, especially of dyeings on wool.

Water-soluble reactive dyestuffs according to the invention which correspond to formula ll and contain advantageously two to five sulfonic acid groups are mainly used, however, for the dyeing and printing of textile fibers containing hydroxyl groups, particularly for natural or regenerated cellulose fibers. Dyeings and prints are obtained which are distinguished by excellent wet fastness properties and good fastness to light by impregnating the textiles with aqueous dyestuff solutions or printing them with thickened dyestufi solutions, drying the impregnated material and treating with acid binding agents, optionally with heating or steaming, and then thoroughly rinsing and soaping.

The dyestuffs according to the invention are also suitable for the dyeing of fibers containing hydroxyl groups by the exhaustion process. During or after the dyeing process which, advantageously, is promoted by the addition of neutral salts such as sodium sulfate or sodium chloride, the dyestufi' is fixed by treatment with acid-binding agents. A particularly simple dyeing process consists in adding the total amount of the neutral salts which promote exhaustion and adding the acidbinding agent to the dye bath from the very beginning, introducing the goods to be dyed at low temperatures (25-40 C.) into the bath, heating the bath gradually to a temperature, depending on the aforementioned starting temperature, in the range of from 40 to 100 C., and continuing treatment at the latter temperature until the fixation of the dyestufi is completed. In this way, dyeings having excellent wet fastness properties and good fastness to light are obtained.

Reactive dyestuffs of formula III wherein Hal is chlorine are fixed at room temperature (about 20 C.) when the bath is strongly alkaline (pH above ll) or, preferably, at elevated temperatures (60 to 160 C.) at lower pH (about 9 to l 1 and those in which Hal represents fluorine are fixed under milder conditions, e.g., at lower temperatures (20 to 30 C.) and/or lower pH (8-1 1 or correspondingly shorter time.

Wet fastness" properties shown by the dyestuffs according to the first and also by those of the second aspect of this invention, described in detail hereinafter, are, in particular, wash fastness, fastness to water, to sea water, to perspiration, and,

in the case of wool dyeings, also fastness to milling and potting. These wet fastness properties are also found in wool dyeings of stronger shades e.g., standard depths 2 to 5 Moreover, the yield rate of fixed dyestuff to unfixed dyestuff portion on wool is very favorable in the case of dyestuffs of the first as well as of the second aspect of the invention.

in the dyeing of cotton and the like cellulose fibers, the unfixed portion of these dyestuffs remaining on the fibers after fixation, can be very readily removed by washing with hot water or by soaping. Wool dyeings are distinguished by level strike of these dyestuffs irrespective of differences in the type of wool, which level strike is assured especially by the use of anionic or nonionogenic dyestuff carriers or mixtures of such carriers.

Preferably sodium or potassium bicarbonates, sodium or potassium carbonates, sodium metasilicate, trisodium phosphate or sodium hydroxide solution, or the sodium or potassium salt of trichloroacetic acid are used as acid-binding agents. In addition the dye liquor or printing paste can contain further additives, for example salts such as sodium sulfate or chloride already mentioned, or auxiliaries such as acid amides, e.g., urea or additives which prevent reduction such as nitrobenzene sulfonic acid, and also additives which accelerate the reaction, such as tertiary amines, e.g., trimethylamine or 1 ,4-diaza-bicyclo-( 2,2,2 )-octane.

Reactive dyestufis according to the invention which correspond to formula [I] and which contain no sulfonic acid group are preferably used in fine aqueous dispersion for the dyeing of hydrophobic fibers, in particular for the dyeing of synthetic polyamide fibers such as nylon.

Further details can be seen from the following nonlimitative examples of this aspect of the invention. Where not otherwise expressly stated, parts and percentages are give by weight. The temperatures are in degrees Centigrade. The relationship of parts by weight to parts by volume is as that of grams. (g) to milliliters (ml.).

18.8 parts of l,3-diaminobenZene-4sulfonic acid are dissolved in 400 parts of water with the addition of sodium carbonate to give a pH of 4.0-4.5, and the solution is cooled to 0-5". 27.7 parts of 2-ethylamino-4-N-chloroforrnylethylamino--chloro-s-triazine dissolved in parw of acetone are added dropwise at this temperature within 15 minutes, the pH of the reaction mixture being maintained at 4.0-4.5 by the simultaneous addition of sodium carbonate solution. As soon as the reaction is completed, 25 parts of aqueous 30 percent hydrochloric acid are added and diazotisation is performed with 6.9 parts of sodium nitrite at 0-5. The suspension of the diazonium compound is poured into a solution of the sodium salt of 28.9 parts of l-(2-chloro- 5'-sulphophenyl)-3-methyl-5-pyrazolone in 200 parts of water and 40 parts of sodium acetate. On completion of the coupling, the new dyestuff is precipitated with sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 40-50. It is a yellow powder which dissolves in water with a greenish yellow color.

The new dyestuff dyes cotton, staple fiber, jute, ramie, hemp, wool, silk, and nylon by the processes usual for reactive dyestuffs in pure yellow shades which are fast to wet and light.

Dyestuffs having similar properties are obtained when, instead of the l-(2'-chloro-5'-sulfophenyi)-3 methyl-5- pyrazolone, an equivalent amount of the coupling components given in the following table 1 are used.

Table 1 Example shades are No. coupling component given in parenthesis 2. l-( 2',5'-disulfoplienyl )-3-methyl-5- pyrazolone, (yellow) 3. l-[ 5',7'-di.sulfonaphthyl-( 2' )-3-methyl- 5-pyrazolone. (yellow) 4. l-(4'-sulfophenyl)-5-pyrazolone-3- carboxylic acid. (yellow) 5. l-( 3-sulfcphenyl3-methyl-5-pyrazolone. (yellow) 6. l-(2'-fluoro-5'-nult'ophenyl)-3-methyl-5- pyrazolone. (yellow) 7. l-ehloroacetylarnino-8-hydroxynaphthalene -4,6-disulfonic acid. (red) 8. l-(B-bromopropionylamino)-8-hydroxynaphthalene-3,6-disulfonic acid. (red) EXAMPLE 9 SOJH (produced by diazotizing 2-aminonaphthalene-4,8-disulfonic acid and coupling the diazonium compound with 1-amino-3- methylbenzene in the presence of alkali metal salts of fatty acids) are dissolved in the form of the sodium salt in 400 parts of water. 29.1 parts of 2-ethylamino-4-N-chloroformylethylamino-6-chloro-s-triazine dissolved in 100 parts of acetone are added dropwise at -25 within 1 hour, the pH of the reaction mixture being kept at-6.57.0 by the simultaneous addition of sodium carbonate solution. As soon as no more free amino groups can be traced, the reaction product is precipitated by the addition of sodium chloride, filtered off and washed with dilute sodium chloride solution. The new dyestuff is dried in vacuo at -50. lt is a yellow powder which dissolves in water with a yellow color. it dyes cellulose and polyamide fibers by the processes usual for reactive dyestuffs in pure yellow shades which have good fastness to wet and light.

Other azo dyestuffs having similar properties are obtained by reacting equivalent amounts of the aminoazo dyestuffs given in the following table 2, in accordance with example 9 with a. 29.1 parts of 2-ethylamino-4-N-chloroformyl ethylamino- 6-chloro-s-triazine or with equivalent parts of the reactant indicated in column 3 of the table, namely b. 2-dimethylamino-4-N-chloroformyl-methylamino-G- chloro-s-triazine,

c. 2-N-methyl-N-phenylamino-4-N-chloroformylrnethylamino-fi-chloro-s-triazine,

d. 2-ethylamino-4-N-chloroformyl-ethylamino-6-fluoro-striazine,

e. 2-(4'-chlorophenoxy)-4-N-chloroformyl-methylamino-6- bromo-s-triazine, or

f. 2-propylamino-4-N-chlorof0rmyl-methylamino--chloros-triazine.

trisulfonic acid-+3-methyl-1- aminobenzenefianiline.

14 4-aminoazobenzenc-3,4-disulfonie a, b, c, d, o, L. D0.

acid 3methyl-l-aminobenzene.

15 2-umin0naphthalone-4,8-disulfonic a, b, c, d, e, f.. Yellow.

disullonle aeid N-methylaniline.

l i-llllllllObOl1Z0ll0-2,4-dlSlllfOlliC n, b, c, d, c, L. Orange.

acid-d-aminonaplithalene-G- sullonic acidi-methyl-3- aminobenzene.

l7 1-aminobenzene-2,5-disullonie acid-nn-aminophenyl urea.

11, b, 0, (1,0, L. Yellow.

50.3 parts of the aminoazo dyestuff of the formula (produced by coupling diazotized 2-amino-4- acetylaminobenzene-l-sulfonic acid with 2-hydroxynaphthalene-6,8-disulfonic acid in an alkaline medium and saponifying the acetylamino group with sodium hydroxide solution, in accordance with the procedure described by Fierz-David and Blangey in Farbenchemie," 8th edition, pg. 283 et seq.) are dissolved, in the form of the sodium salt, in 800 parts of water witha neutral reaction. 30.6 parts of 2- dimethylamino-4-N-chloroformyl-n-butylamino-6-chloro-striazine dissolved in parts of acetone are added at l5-20 the pH of the reaction mixture being kept at 5-55 by the addition dropwise of sodium carbonate solution. As soon as no more diazotizable amino groups can be traced, the dyestuff is completely precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 60-70. lt dissolves easily in water with an orange color and dyes polyamide and cellulose fibers by the processes usual for reactive dyestuffs in yellowish orange shades.

By reacting the aminoazo dyestuffs listed in the following table 3 according to the procedure described in example 18 with, in each case,

a. 2-dimethylamino-4-N-chlorofonnyl-n-butylamino-6- chloro-s-triazine or with equivalent parts of b. 2-methoxy-4-N-chloroformyl-ethylamino-6-chloro-striazine,

c. 2-phenoxy-4-N-chloroformyl-methylamino-6-chloro-striazine,

d. 2-morpholino-4-N-chloroformyl-methylamino-6-bromos-triazine,

e. 2-(4'-methoxy-phenoxy)-4-N-chloroformyl-ethylamino- 6-chloro-s-triazine,

f. 2-(4'-chlorophenylamino)-4-N-chloroformylmethylamino-G-chloro-s-triazine and g. Z-dimethylamino-4-N-chlorofonnyl-methylamino-6- chloro-s-triazine, respectively valuable dyestuffs are obtained, dyeings of which on cellulose fibers yield the shades given in the last column of table 3 below.

phonic acid, saponified.

TABLE 3Continued Shade on cellulose Example No. Aminoazo dyestuffs fibers 23 (a to g) 1-aminobenzene-2,5-disulphonic acid alkaline Orange.

2-aiixlno-5-hydroxynapthalene-7-sulphonic 24 (a to g) 2-aminonaphthalene-l,fi-disulphonic acid Reddish alkaline 2-methylamino-5-hydroxynaphorange.

thalene-7-sulphonic.

25 (a to g) 1-amin0benzene-2,4-disulphonic acid1- Red.

(3-aminobenzoylamino)-8-hydroxynaphtha1ene-3,6-disulphonic acid.

26 (a to g). 2-amino-4-acetylaminobenzene sulphonic Orange.

acid- 2-aminonaphthalene-S,7-disulphonic acid saponified.

27 (a to g) 2-amino-4-acetylamin0benzene sulphonic Yellow.

acid-*l-(W-sulphophenyl)-3methy1-5- pyrazolone, saponified.

28 (a to g)..." 2-amino-5-nitrobenzene sulphonlc acid1- D0.

(3-su1pho henyl)-3-methyl-5-pyrazole imine, re ucad.

29 (a to g). 1-amino-3-nitr0-6-ethylbenzene+l-hydroxy- Reddlsli naphthalone-3,6-disulfonic acid, reduced. orange.

30 (a to g) l-am no-3-N-methylsulfamylbenzene-d- Red.

amin-8-hydr0xynaphthalene-3,fi-dlsulionic acid.

31 (a to g) l-aminobenzene-iS-N-('y-hydroxypropyl)-N- Red.

methylsulfonamidel-amino-S-hydroxynaphthalene-3,6-disulfonic acid.

32 (a to g) 4-amino-3-carboxy-benzene-sulfonic acid- Orange.

2-ag1ino-5-hydroxynaphthalene-7-sulfonlc ac 33 (a to g) 1-arninobenzenc-3-N-(Bhydroxyethy1)-N- Red.

methylsulionamide- 1-amlno-8-hydroxynaphthalene-4,G-disulfonic acid.

34 (a to g) 3-amin0-4-ethoxybenzene-sulfonic acid Orange.

2-zirdnino-5-hydroxynaphthalene-7-sulionlc ac 35 (a to g) l-aminobenzene-3-N-(fi-sulfoethyl)-N- Red.

methylsulionomaidefil-amino-8-hydroxynaphthalene-3,fi-disulfonic acid.

36 (a to g) 2-amin0naphthalene-4,6,8-trisuli0nic acid- Yellow.

1-(4 -aminophenyl)-3-methyl-5-pyrazolone.

37 (a to g) l-amino-3-N,N-bis-('y-hydroxypropyD-sul- Red. farnyl-benzenel-amino-S-hydroxy- Red. naphthalene-3,6-disulfonic acid.

38 (a to g) 2,3-diamino-diphenyl-1,1-disulfimide- 1- Red.

amino-B-hydroxynaphthalene-3,6- disulfonic acid.

39 (a to g) Z-aminonaphthalene-l,5,7-trisulionic acld Red.

2-amino-5-hydroxynaphthalene-7-sulionic acid-el-amino-3-methylbenzenc.

40 (a to g) 2-amino4-nitrobenzene sulfonic acid-vl- Red.

benzoylarnino-8-hydroxynaphthalenei, disulionic acid, reduced.

As used in the above Table 3 and subsequent tables, a1; kaline means that the coupling was carried out in a conventional manner at a pH above 7, saponified" means that the coupled product was treated as described in example 18, supra, and reduced means that the coupling product was treated as described in example 4011, infra.

EXAMPLE 40h I110 1IIHOO N=Nf HOaS SOaH 62.2 parts oi the sodium salt oi the aminoazo dyestuii of the formula (obtained by coupling diazotized 2-amino-4-nitrobenzene sulfonic acid with l-benzoylamino-8-hydroxynaphthalene-3,6-

disulfonic acid in a neutral medium and reducing the nitroazo dycstuff with sodium sulfide in alkaline medium of pH about 10-12) are dissolved in 500 parts of water. At l5-20, 29.0 parts of 2-ethylamino-4-N-chloroformyl-ethylamino-6-chloros-triazine dissolved in parts of acetone are added dropwise, the pH of the reaction solution being kept at 5.0-5.5 by the addition of sodium carbonate solution. As soon as no more free amino groups can be detected, the dyestutf is completely precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 6070. lt dissolves easily in water with a red color and dyes cellulose and polyamide fibers by processes usual for reactive dyestuffs in pure red shades.

51.7 parts of the copper containing aminomonoazo dyestufi of the formula (obtained by coupling diazotised 2-amino-l-hydroxybenzene- 4,6disulfonic acid with 2-amino-S-hydroxynaphthalene-7sulfonic acid in an alkaline medium and treating the aminomonoazo dyestuff obtained with an agent giving off copper) are dissolved, in the form of the sodium salt, in 1,000 parts of water. At 010, a solution of 27.6 parts of 2- methylamino-4-N-chloroformyl-methyl-amino-6-chloro-striazine in parts of acetone is added and the pH of the reaction solution is maintained at 5.5-6.0 by the addition of sodium carbonate solution. As soon as no more free amino groups can be traced, the new dyestuff is completely precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 4050. It is a dark powder which dissolves in water with a ruby red color.

it dyes cotton, staple fiber, jute, ramie, hemp, wool, silk and nylon by the processes usual for reactive dyestuffs in pure ruby red shades which are wet fast.

Further metal-containing aminoazo dyestufis are given in the following table 4 which are reacted as described in this example with a. 2-methylamino-4-N-chloroformyl-methylamino-6- chloro-s-triazine or with equivalent parts of b. 2-ethylamino-4-N-chloroformyl-ethylamino-6-chloro-striazine,

c. 2-ethoxy-4-N-chloroformyl-methylamino-6-chloro-sv triazine,

TABLE 4 Shade on cellulosev Example No. Metal-containing aininoazo dynstulis Illn'cs 42 (n to l). .Z-umllio-l-hydroxyhonzcnc-4, 6- lisulphouic Violet.

ncld llikliliilll l-nmino-ii-hylll'oxynuphih- TABLE 4 -(.ontinued EXAMPLE 56 Shade on cellulose H Example N 0. Metal-containing aminoazo dyestuffs fibres H03 S S 03H alene-3, G-dlsulphonic acid, copper 5 complex. (3,11

43 (a to f) 2-amino-1-hydroxybenzene-4-sulphonic acid- Bordeaux.

alkaline 2-amino-8-hydroxynaphthelene-G- U l O NH- -NH.CON NH.C2H: sulphonic acid, copper complex. I 44 (a to f) 6-nitro-1-amino-2-hydroxynaphthalenei- Black. N N

sulphonic acid alkaline 2-amino-5- 10 S 0 11 hgdrozicynaphthzalene-g-sulphonic acid, Y 0 rom urn comp 8X I I 45 (a to 0.. 4-nitro-2-amln0-l-hydroxybenzene alkaline Do. 569 parts of l amino 4 (4l aminophenylamino)- 1'amino-8-hydloxynaphthalene-3,6- anthraquinone-2,2,7'-trisulfonic acid (obtained by sulfonadisulphonic acid, chromium complex 1:2.

46 (a to f) 4-nitro-2-amino-l-hydroxybenzene alkaline Black- (4 ammophenylammo) mhraqulpone brown. 2,7-dlsulfomc acid in 30 percent oleum) are dissolved, in the l-amino-S-hydroxynaphthalene-3, 6- disulphlmic acid cobalt complex 112' form of the sodium salt, In 1,000 parts of water, A solut on of 47 (a to f) 2-amlno-4acet lamlno-ihydrogrybenzone-fi- Reddlsh 27.7 parts of 2-ethylammo-4-N-chloroformyl-ethylammo-G- sulphomc alkalm g gs chloro-s-triazine in 100 parts of acetone is added to this solu- 2530;352:221zggggfihiisulphonic acid, Lion :ropwisle at 2025:1and flit; pH is maintzined at 583-5? 48 (a to f) 2-amino-4-acetylamino l-hydroxybenzene-fi- Navy blue. I y t slmu i' o Iumdcar a? i sulphonic acid alkaline 1-pheny1amino-8- solution. On comp etion 0 e reaction, cedrlew yfesgi o hy droxynaphthTe 1 fimsulphoni c d the above formula 15 precipitated by the a won 0 s rum copper complex, saponified. chloride, filtered off, washed wlth aqueous sodium chloride 49 (a to 3 2 333 gggg g gggggeg Bluesolution and dried in vacuo at 40-s0. it dissolves in water with a blue color and dyes cotton, staple fiber, jute, ramie, pg g g g gg -fi *disulpmmic acid hemp, wool, silk and nylon by the processes usual for reactive om 6X.

50 (a to I)..." 2-amino-fiawg aminoi-hydroxybenzene- Ruby red. ye tuffs 1n et-fast blue shades.

Q acid-)Phydmxy naphthalene" Other aminoanthraquinone dyestuffs listed in the following 5 acid copper complex table 5 are condensed as described in example 56 with sapom e 51 to 0"... -a Iran-6 a etygaraliagligg qg n gel a. 2-ethylammo-4-N-chloroformyi-ethylammo-6-chloro's- SH 0 08.0 sup op any IOWl'l. 3-rriethyl-5-pyrazolon e, copper complex, tnazme or fquwalcm pan8 of saponified. b. 2-methyltluo-4-N-chloroformyl-methylammo-6-chloro-s- 52 to l).. l-hylroxy-2-an}:irgz-5-methygiskulionygbgnzene Ruby. M e 1 am no-8- roxyna a enedisulionic acid copper omplex. c. 2-d1ethylanuno-4-N-chlorofonnyl-methylam1no-6- 53 (a to i)..... 3-aNm(lno-4-l;ydr%xy-bl(;nzoliulioiiic aciila 1d Yellow. chlro s mazine,

3-am nop eny -ace oace cac am e 1:2-cobalt complex. d. 2-N-methyl-N-(4 -chlorphenylamino)-4-N-chloroformyl- 54 o 3-hydroxy-4-amino-bromobenzol 1-amln0- Violet. b 1 fl 6 h| i i 55 (a to f) 1my???-2-arriinofbenz i g 'lfi y' Rubyf. 2-phenylamino-4-N-chloroformyl-ethylamm0-6-chloro-s- 6 y EXHY S11 onam 6-) -ammohydroxynaphthalenea, Misuuonic acid, trraz1ne, respectwely."lhe shade of the cellulose dyemgs ob pp p tamed with the resulting reactive dyestuffs IS given in the last W u A, o 7 column of table 5.

TABLE 5 Shade on Example cellulosev No. Aminoanthraquinoue dycstuff ll hrcs 57 0 NH; Bled 58 O NIIg D0- 59 O NlIg Dr).

W TABLE 5 ConIiU r Shade on Lxampln cellulose N n. Aminoanthraquinone dyestufi fibres (H! Nll' Do.

I! I O NH S H 61 O NHg D0- EXAMPLE 62 57.6 parts of copper phthalocyanine tetrasulfonic acid chloride are slurried in 500 parts of water and 300 parts of ice. Fifteen parts of rn-aminoacetanilide are stirred in and the pH is adjusted to 7 by the addition of aqueous ammonia solution. The temperature is allowed to rise slowly to 40-50, the pH of the suspension being maintained at 7.0-7.5 by the dropwise addition of ammonia solution. As soon as no more primary amine can be traced, 270 parts of 30 percent hydrochloric acid are added and the mixture is heated for 3 hours at 8590 In this way the acetyl-amino group is saponified.

The amino-phthalocyanine dyestuff of the formula wherein Pc represents the phthalocyanine structure is so obtained.

This dyestuff is then isolated by filtration, again slurried in 1,000 parts of 0-5 cold water and the pH of the suspension is adjusted to 8.0 with dilute sodium hydroxide solution. A solution of 27.7 parts of 2-ethylamino-4-N-chloroformyl-ethylamino-6-chloro s-triazine in 100 parts of acetone is poured into this suspension. Condensation is performed at l-20 while stirring well and the hydrochloric acid liberated is neutralized by the dropwise addition of dilute sodium carbonate solution. On completion of the reaction, the new dyestuff is completely salted out, filtered off and dried in vacuo at 50-60. It corresponds to the formula SOz-NH- CuPc the following table 6, are condensed as described in example 62 with a. 2-ethylamino4-N-chloroformyl-ethylamino--chloro-striazine, or with equivalent parts of b. 2-piperidino-4-N-chloroformyl-methylamino-6-chloro-striazine,

c. 2-dimethylamino-4-N-chloroformyl-ethyl-amino-6- chloro-s-triazine,

d. Z-dibutylamino-4-N-chloroformyl-methyl-amino-6- chloro-s-triazine,

e. 2-( 4-methylphenylamino )-4-N-chloroform ylmethylamino-6-chloro-s-triazine, and

f. 2-N-methyl-N-(4-methylphenylamino)-4-N-chloroformyl-methylamino--bromo-s-triazine, respectively.

acid are dissolved in 400 parts of l5-20 warm water and the pH is adjusted to 6.5 with sodium hydroxide solution. A solution of 30.6 parts of Z-N-methyl-N-ethylamino-4-N-chloroformyl-ethyl-amino-fi-chloro-s-triazine in parts of acetone is added dropwise to this solution within 15 minutes and the pH of the reaction mixture is kept at 4.5-5.5 by the addition of sodium carbonate solution. When no more diazotisable amino groups can be traced, 30 parts of sodium bicarbonate are added to the solution and then a solution of 30.3 parts of diazotised Z-aminoaphthalene-l ,S-disulfonic at acid is poured in. As soon as the coupling is complete, sodium chloride is added to the reaction mixture, the precipitated dyestuff is filtered off and washed with sodium chloride solution. After drying at 60-70, a red powder is obtained which dissolves easily in water with a red color.

If cotton or staple fiber is dyed or printed, by the processes usual for reactive dyestufis, with this dyestuff then red dyeings or prints are obtained which have very good properties.

Other dyestuffs having similar properties are obtained if the coupling components containing acylatable amino groups given in the following table are condensed as described in example 65 with a. 2-N-methyl-N-ethylamino-4-N-chloroformyl-ethylamino- 6-chloro-s-triazine, or with equivalent parts of b. 2-ethylamino-4-N-chloroformyl-ethylamino-6-fluoro-striazine, and coupled with the diazo components also given in the table 7.

parts of sodium nitrite. The suspension of the diazonium compound is poured into a solution of the sodium salt of 28.9 parts of l-(2-chloro-5'-sulfophenyl) in 200 parts of water and 40 parts of sodium acetate. As soon as the coupling is complete, the pH of the dyestufi' solution is raised to 7.0 and the new dyestuff is precipitated by the addition of sodium chloride. Also, l9.5 parts of a mixture of anhydrous primary potassium phosphate and anhydrous secondary sodium phosphate in a weight ratio of 1.8: l .0 are added.

The mixture is stirred for 1 hour and the precipitate is filtered off, washed, and mixed with l 1.7 parts of the mixture of anhydrous primary potassium phosphate and anhydrous secondary sodium phosphate mentioned above and dried in vacuo at a temperature under 45.

The monoazo dyestuff so obtained is a yellow powder which dissolves in water with a greenish yellow color.

The 2-ethylamino-4-N-chloroformyl-ethylamino-6-fluoro-striazine used as starting material is obtained by reacting 2,4-

TABLE 7 Example Coupling components containing Shade on N o. Diazo component acylatable amino groups cotton 66 (a-b) 1-aminobenzene-2, fi-disul- 1-amino-8-hydroxynaphthalcne- Red.

phonic acid. 3, 6-disulph0nic acid.

67 (a-b) 2-amin0naphthalenc-l, 5- s. d Bluish red.

disulphonic acid.

68 (a-b) s l-aminobenzene-izl-amino-B-hydroxynaphthalenc- Red.

sulphonic acid. 4, G-disulphonic acid.

60 (21-1)) 1-aminobenzene-2,4- 1-(4aminophenyl)-3-rncthyl-5- Yellow.

disulphonic acid. pyrazolonc.

70 (a-b) 1-aminobcnzene-2, Z-amino-S-hydroxynaphthalcnc- Orangc.

disulphonic acid. 7-sulphonic acid.

71 (a-b) 4-aminoazobei1zcnc-3,4 2-methylamino-fi-hydrozy- Scarlet.

disulphonic acid. naphthalcne-7-Sulphonic acid.

72 (a b) 2-aminonaphthalenc-1,5- 1-amino-8-hydroxynaphthalcimlllulsh rod.

disulphonic acid. 4, fi-disulphonic acid.

EXAMPLE 73 bis-ethylamino-ti-chloro-s-triazine with potassium fluoride in dimethyl formamide to form 2,4-bis-ethylamino-6-fluoro-striazine and treating the latter according to known methods with phosgene in toluene.

By padding cotton at room temperature with a 2 percent aqueous solution of this dyestuff which also contains 20 parts of sodium carbonate and 50 parts of sodium sulfate per liter, rolling up the impregnated goods, wrapping in a plastic cover and keeping for 4 hours at 2$-30 and finally soaping at the boil for 30 minutes, then a yellow dyeing is obtained which has very good fastness to washing and light.

Dyestufis having similar properties are obtained, in accordance with the preceding example, by condensing the diaminobenzene sulfonic acid compounds given in column ll of the following table 8 with equivalent parts of the acylating agents given in column ll] of said table; the condensation products are then diazotized and the resulting diazonium compounds are finally coupled with the coupling components listed in column W. The shade on cellulose fibers obtained with the final products is given in the last column of table 8.

TABLE 8 II ill lV Diaminobenzenc Shade on Ex. sulphonic acid cellulose pound Aeylating agent Coupling component bflS 74 1,3-diaminobenzene-4- F N NHC H 1-(2,5-di ulphophcnyl)-3 nicthyl-dpymzolonc Yullcw.

sulphonic acid. Y

N-COC1 CzHs 75 o Same as above 1-(2,5-dichloro-4-su1phophcnyl-3-mcthyl-5-I yra olonc. 76 0 .do l 1-(3- ulphophcnyl)3-methyl-5-pyraZ0l0l1c M 77 .do 1-[5,7-disulphonaphthyl-(2)]-3methyl 5-pyrazo1onc. Do. 78. "do. .1-[4,8-disulphonaphthyl-(2)-3-mcthyl-5pyrazolonc. Do. 70... .do 1-(4- u1phophcnyl)-5-pyrazolone-3-carboxy l Dov 79 ..d0 V 1-(4- ulphophcnyl)-5-pyrazolonc3-ca1-hoxylic acid. Do. Pill. .4-(llzunlnl .lzc c-3- d() t v V 7 4 7 V 7 d V I 7 4 V 7 Do.

sullphonlc acid. M to... Z-di1nothylurnlno-4-N-chlorol'ormylmcthyldo.

umin0-6-fluoro-s-t1-iazinc. H2. l,Zl-diaminobcnzcnn t do d0 sullonlc acid. 83 ......do 2-propylamino-4-N-chlorol'ormylmuthylnmino-(ll-(2,5-dlsulfoplunlyl)-3-mcthyl-6-pyrazolonc D lluoro-s-triazinc.

TABLE 8-Continued ll Ill lV E Dilaikiliinobenzdene sllilmllu on X- 811 p Ol'llC 210i ('0 ll 051. N0. compound Acylatlng agent Coupling component lilnvs 84 Mdo." ii-(Hillylthioi-N-ehlorolormylhutylmnlnofil-(2,5-dichloroW- ullophonyl)-3-methyl-5- uoros-tfiazinv. pyram mm. 85 "do 2-nl1eLhoxy-4-N{chloroformylmothylinnlno-ti- 1- 3- ultoplmnyl)-3-methyl-E-pymzolone... V

iuoro-s-trinz no. 86 do... 2-phenoxyi-Nichloroformylnwthylmnlno-sl-[,7-disulfonuphthyl-(2)1-3-nmthyl-5-pyralOlOI Ilu0r0-s-trinz no. 87 .110 2-ethoriy-4-N-chlm-oformylethylanilno-(i-lluom- I-[4,8-di ulfomiphthyl-(2)I-K-nwthyl- -nyra triziz no. clone. 88 -d0. 2-aflmylaminpfiN-chloroformylmethylamlno-fil-(4-sulfophonyl)-5-pyraZ0lone 3-carboXyl c a uoro-s-tr 212 no. 8 2-r1l1ibutylaminpA-N-ehlor0forn1ylmethylamino-(i- 1-(2-fluoro-b-sulfophcnyl)-3-methyl-fi-pyrazolone. Do.

HOrO-s-triaz ne. 90 -d0 2112bOnylamllIO-IN-ChlOIOi OI'mYll'l](ltllylallllll0-fi 1431loroaeetylarlinohydroxynaphthalen uoro-s-tr azine. isulionic aci 91 0 2-N-methyl-N-othylamino-4Nchlorol'0rmyl- 2-(fl-bromopropionylamino)-8-hy r0 Y aD Scarletmethylamino-G-fluoro-s-triazine. thalene-3,6-disulionic acid. EXAMPLE 92 TABLE 9-Conlinucd Shade on S 03H CH3 Example cellulose Number Aminoazo dyestuif fibres NN- NHCO 1i: N\ F r a I I ainino-B-methoxybenzene.

I 96. (a-d) 2-aminonaphthalene-4,S-disulphonio acid l- D0. CH3 N N N-methylaminobenzene. 97. (a-d). Z-aminonaphthalene-4,6,8-trisulphonic acid- 1- DO.

I aminobenzene. S 03H NHCH3 98. (a-d) Z-arninonaphthalene-4,6,8trisulphonie acid-+1- Orange. 7 V J 7 9 d) amino-3-rlgiethylbenzerael-aminobenenf. D

J. a- 4-aminoaz0 e ene-3,4- sul honic uci 0. 42.1 parts of the sodium salt of the aminoazo dyestufi obamino.3.mefiy1bemene: p A tained by coupling of diazotized 2-aminonaphthalene-4,8- -d)- la r ignggg t l igg ggg 2 1 3515:gggg rwd- 0- disulfonic acid with l-amino-3-methylbenzene are dissolved in me thyl-3-amino-ber 1zene. 400 parts of water and the solution is cooled to 0-5. 24.2 (a'dlm -i g rgz esri g f f g sult a -*G- Yellowparts of 2-methylamino-d-N-chloroformybmethylamino-6- fluoro-s-triazine dissolved in l00 parts of acetone are added EXAMPLE 102 dropwise to the solution within 30 minutes at this temperature and the pH of the reaction mixture is kept at 6.5-7.0 by the on 110 s simultaneous addition of sodium carbonate solution. As soon as no more free amino groups can be traced, a solution of 40 -N=N parts of a mixture of primary potassium phosphate and secon- N dary sodium phosphate (weight ratio 1.8:!) in 200 parts of -SOa NHCON F water is added to the reaction mixture. The new dyestutf is N N precipitated by the addition of sodium chloride, after stirring 40 S 03H for 30 minutes it is filtered off and washed with dilute sodium chloride solution. The filter residue is mixed with 12 parts of a NHCZHJ mixture of anhydrous rim otassium hos hate and an- 50.3 )arts of the sodium salt of the aminoazo dyestuff P P P P I hydrous secondary sodium phosphate (ratio 1.821) and dried 0f the formula in vacuo at a temperature under After drying, the dyestuff 45 OH H03 s is a yellow powder which dissolves in water with a yellow color. N N

Four parts of the new dyesturf are dissolved in 1,000 parts of water and 20 parts of sodium carbonate are added. One- S 03H NH: hundred parts of cotton are entered at 20 and the bath is heated to 40 within 30 minutes, 80 parts of sodium chloride $9 .3 W W W W are added to the solution and the goods are dyed for 1 hour at d 2 4 this temperature. The dyeing is then rinsed and soaped at the ba "F;' j: 2: 3; boil for 15 minutes. A deep yellow dyeing is obtained which ace gl 2 3? s lk y d has good fasmess to water andlight ynap one; lsul onlc acl m an :1 a 126: mehltzm sa on' in e acct amino rou wi so ium l'OXl e Other-am dyeSt-ufis having Slmfla-r prqpemes are -obtamed sol utit a ri l a rc dissolvelil with a eutr al reaction in 800 parts of 3 iz the g: dyestuffs gwen m the followmg table water Twenty-six parts of 2-ethylamino-4-N-chloroformylin e manner descri d in example 92, with thylamino-6-fluoro-s-triazine dissolved in 100 parts of a. 2-meth n e Smiazine i zgl sfg g methylammo 6 fluom acetone are added to this solution at 0-5, the pH of the reacb dimeth ino chl r form I meth l ino 6 tion solution being kept at 5-5.5 by the dropwise addition of fluo'ro s triazine y m o O y y am sodium carbonate solution. when no more diazotisable amino groups can be traced, the dyestuff is completely precipitated t ethylamm0'4'N cmorofmmyl'n'butylammn'6'fluoro's' by the addition of sodium chloride, isolated, stabilized with nazmeor buffer salts and dried in vacuo at 40. it dissolves easily in d. Z-N-methyl-N-phenylam1no-4-N-chloroformylwater with an Orange color methylamino-o-fluoro-s-tnazme. lf cotton or staple fiber is printed by one of the usual TABLE methods with a printing paste consisting of 30 parts of this J dyestufi, 200 parts of urea, 400 parts of water, 350 parts of 5 Fmm 1e 3 on percent aqueous sodium alginate solution and 20 parts of ,11, ,61,. Aminoazo dyeswfl potassium carbonate, then dried, steamed for 10-15 minutes, then rinsed and finally soaped at the boil, an excellent wash- JJ. tat-d) 2*lliillkglllplltlllllilllwfi,7-dl$lllpll0lll0 acid-d- Yellow. fast orange p is obtained \lll [l0 (llZtllQ- 'Jl. m-dL. .Anninonpphtlialoned.B-disifilghonic acld 1- Do. By reacting equivalent amounts of the aminoazo dyestuffs amiuo-L-met ioxy met my enzene. 5. oHlL... Laminonaphthaleneo,S-disulphonic acid-d Do m the followmg table In accordance wlth the 2 i procedure described in example 102, with a. 26 parts of Zethyl-amino- LN-chloroformyl-ethyl-amino- 6-fiuoro-s-triazine, or with equivalent parts of b. Z-dimethylamino-4-N-chloroformyl-n-butylamino-6- fluoro-s-triazine,

c. 2-N-methyl-N-phenylamino-4-N-chloroformylethylamino-o-iluoro-s-triazine,

d. 2'dimethylamin0-4-N-chloroformyl-isopropylamino-(S- fluoro-s-triazine,

e. 2-(4-chiorophenylamino)-4-N-chloroformylmethylamino-6-fluoro-s-triazine,

f. 2-(4'-methylphenylamino )-4-N-chlorofonnyl- TABLE 10 Shade on cellulose Example N o. Aminoazo dyestufl" fibres 103 (a-g) 2-amino-4-nitrobenzene sulphonic acid Red.

1-benzoylamino-8-hydroxynaphthalene-4,6- disulphonic acid, reduced.

104 (a-g) 2-amino-4-nitrobenzcne sulphonic acid- Red.

l-acetylamino-S-hydroxynaphthalene-3,6- disulphonic acid, reduced.

105 (a-g) 2amino-4-nitrobenzene sulphonic acid Red.

1-benzoylamino-8-hydroxynaphthalene-B, 6-disulphonic acid, reduced.

106 (ag) 2-amino4-acetylaminobenzene sulphonic Orange.

acid l-hydroxynaphthalene-3,6-disulphonic acid, saponificd.

107 (a-g) 2-amino-4-acetylaminobenzene sulphonic Redacid l-hydroxynaphthalene-4,6-disulorange. phonic acid, saponified.

108 (a-g) l-aminobenzene-2,4-disulphonic acid alkaline Orange.

2-ainino-5-hydroxynaphthalene-7-sulphonic ac 109 (a-g) Z-aminonaphthalene-LB-disulphonic acid Reddish alkaline 2-methylamino-5-hydroxyorange. e naphthalene-7-sulphonic acid.

110 (a-g) l-aminobcnzene-2-sulphonic acid 1-(3- Red.

amino-benzoylamino)-8-hydroxynaphthalene-3,6-disulphonic acid.

111 (a-g) 2-amlno-4-acetylaminobenzene sul honic Orange.

acid+2-aminonaphthalene-5,7-d sulphonic acid, saponified.

112 (a-g) 2-amino-4-acetylaminobenzene sulphonic Yellow.

acid 1-(3sulph0phenyl)-3-methyl-5- pyrazole imine, saponificd.

113 (a-g) 1-amino-3-nitro-G-etl1ylbenzenel-hydroxy- Raddish na hthalene-3,6-disulfonic acid, reduced. orange.

114 (a-g) l arn nobonzene-3-N-methylsulfamidewb Red.

amino-S-hydroxynaphthalene-3,6-disulionic acid.

115 (a-g) 1-aminobenzene-3-N-(y-hydroxypropyD-N- Red.

methylsulfonamide l-amino-8-hydroxy naphthalene-3,6-disulionic acid.

6 -g) 4-amino-3-carboxy-benzene sulfonic acid- Orange. 2-amino-5-hydroxy-7-sulfonic acid.

117 (a-g) 1-aminobenzene-3-N-(fl-hydroxyethyl)-N- Red.

methylsulionamidel-aminO-S-hydroxynaphthalene-4,G-disulionic acid.

118 (a-g) 3-amino-4-ethoxybenzcna-sulionic acid- Orange.

Z-drininOS-hydroxynaphthalene-7'sulfonic ac 119 (al-aminobenzene-3-N-(fl-sulfoethyl)-N- Red.

methylsulfonamide 1-amino-8-hydroxynaphthalene-3,6-disulionic acid.

120 (a-g) 2-aminonaphthalene-4,6,8-trisulionic acid- 1- Yellow.

(4-aminopheny1)-3-methy1-5-pyraz0lona.

121 (ag). 1-aminobenzene-3-N,Nbis-( -hydroxy- Red.

propyl)-sull'onamide 1-amin0-8-hydroxynaphthalene-3,o-disulfonic acid.

122 (a-g) 2,3-diamino-diphenyl-1,1-disulfimide- Red.

lbenzoyl-amino-8-hydroxynapthtalene-3,6- disulionic acid.

123 (ag) 2-arninonaphthalcne-l,5,7-t1'isulionic acid 2-amino-5-hydroxynaphthalene-7-sulionic acid+1amino-S-methylbenzene.

Red.

22 5 l.7 parts of the sodium salt of the copper-containing aminomonoazo dyestuif of the formula HOaS (obtained by coupling diazotized 2-amino-l-hydroxybenzene- 4,6-disulfonic acid with 2-amino-5-hydroxnaphthalene-7-sulfonic acid in an alkaline medium and treating the aminomonoazo dyestuff obtained with an agent giving off copper) are dissolved in 1,000 parts of water. At 05, a solution of 27.2 parts of 2-ethylamino-4-N-chloroformylethylamino-6-fluoro-s-triazine.in 100 parts of acetone is added and the pl! of the reaction solution is kept at 5-5.6 by the addition of sodium carbonate solution. When no more free amino groups can be traced, the new dyestufi is completely precipitated by the addition of sodium chloride, buffer salts are added and the dyestuff is isolated and dried in vacuo at The dark powder dissolves in water with a ruby red color.

If cotton is padded with a 2 percent solution of this dyestuff which also contains 2 percent of sodium bicarbonate, the impregnated goods are stored for 4 hours at room temperature, then soaped at the boil, and rinsed, a ruby red dyeing is obtained which has very good wet and light fastness properties.

Other metal-containing aminoazo dyestuffs are given in the following table I l, which are reacted as described in example 124 with -a. Z-ethylamino-4-N-chioroformyl-ethylamino-6-fluoro-striazine, or with equivalent amounts of b. 2-N-methyl-N-ethylamino-4-N-chloroformyl-ethylaminoacid alkaline .Z-amino-5-hydroxynaphthalenc 7-sulphonic acid, copper complex. 128 (a-c) 2-amino-1-hydroxybenzeneA-sulphomc acid alkaline Z-N-methylamino-fi-hydroxynaphthalene-7-sulphonic acid, copper complex.

129 (a-c) fi-nitro-i-amino-2-hydroxynaphthalene-4- sulphonic acid alkaline 2-amino-5-hydroxy- Black.

naphthalene-7-sulphonic acid, chromium complex 1:2. 130 (a-c) 4-nitro-2-arnlno-l-hydroxybenzene alkaline Do.

1-amino-8-hydroxynaphthalene-3,6- disulphonic acid, chromium complex 1:2. 131 (a-c) 4-nitro-2-amino-1-hydroxybenzene alkaline Blackbrown. l-aminoS-hydroxynaphthalene-3,6- disulphonic acid, cobalt complex 1:2. 132 (a-c) 2amino-4-acctylamino-l-hydroxybcnzcno-fisulphonic acid alkaline 1-amino-8- hydroxynaphyhalenc-2,4-disulphonic acid, copper complex, saponificd. 133 (a-c) 2-amino-4-acetylamino-l-hydroxybenzene-fisulphonic acid alkaline 1-phenylamino-8- hydroxynaphtl1alene-4,6-disu1phonic acid, copper complex saponified.

134 (a-c) G-nltro-l-amino-Z-hydroxynaphthalene-isulphonic acid alkaline l-amino-B-hydroxy- Reddish navy blue.

Navy

blue.

Blue.

naphtlialene-2-,4-disulphonic acid, reduced, copper complex.

Example N0. Metal-containing aminoazo dyestuffs 2-amino-G-acetylamino-1-hydroxybenzene-4- Ruby red.

sulphonic acid l-hydroxynaphthalenel, G-disulphonlc acid, copper complex, saponified.

Z-amino-6-acetylamino-l-hydroxybenzeneA- sulphonic acid- 1-(2,5-disulphophenyl)-3 methyl-B-pyrazolono, copper complex saponified.

1-hydroxy-2-amino-5-methylsulfonylbenzene Ruby red.

2amino-8hydroxynaphtha1ene-3,6- disulfonic acid, copper complex.

3-amino-4-hydroxybenzcne sulfonic acid N-(3-amlnophcnyl acetyl acetic acid amide, cobalt complex 1:2.

3-hydroxyA-amlno-bromobenzene- 1-amin0- 8-hydroxy-3,6-dlsulfonic acid, copper complex.

1-hydroxy-2-aminobenzene-5-N-(fi-methoxyethyl) -N-amylsulfonamide- 2-amino-8- hydroxynaphthalene-3,6-disulfonic acid, copper complex.

Yellowbrown.

138 (21-0) Yellow.

139 (a-c) Violet.

140 (a-c) 1 Ruby red.

EXAMPLE 141 HOaS 48.9 parts of l-amino-4-(4'-aminophenylamino)- anthraquinone-2,7-disulfonic acid are added at 20-25 in 500 parts of 30 percent oleum. The reaction mixture is stirred for 24-36 hours at 20-25. The reaction mixture is then poured onto ice and the dyestufl' which precipitates of the formula The filter cake, in the form of the sodium salt, is dissolved in 1,000 parts of water. A solution of 26 parts of 2-ethylamino-4- N-chloroformyl-ethylamino--fluoro-s-triazine in [00 parts of acetone is added dropwise to this solution at 0-10 and the pH is kept at 5-5.5 by the simultaneous addition of sodium carbonate solution. On completion of the condensation, the

new dyestuff is precipitated by the addition of sodium chloride, isolated, stabilized with buffer salts and dried in vacuo at 40 It dissolves in water with a blue color.

If regenerated cellulose is padded with a 2 percent solution of this dyestuff which also contains 10 g. of sodium bicarbonate and g. of urea per liter, the impregnated goods are dried and heated for 2 minutes at l00-l 10, then a pure blue dyeing is obtained which has very good fastness to washing and light.

Other aminoanthraquinone dyestuffs are given in the following table 12 which are condensed as described in example 141 with a. 2-ethylamino-4-N-chloroformyl-ethylamino-6-fluoro-striazine, or with equivalent parts of b. 2-diethylamino-4-N-chloroformyl-methylamino-6-fluoros-triazine,

c. 2-methylamino-4-N'chloroformyl-methylamino-6-fluoros-triazine.

d; 2-N-methyl-N-(4'-chlorophenylamino)-4-N-chloroformyl-methylamino-6-fluoro-s-triazine,

e. 2-N-methyl-N-(4'-ethoxyphenylamino)-4-N-chloroformyl-methylamino-6-fluoro-s-triazine, or

f. 2-phenylthio-4-N-chloroformyl-ethylamino--fluoro-striazines, whereby reactive dyes of similar properties as those described in the preceding examples are obtained. Cellulose fibers dyed therewith have the shades given in the last column of table 12.

TABLE I2- Continued 140 m-n Nil; 00.

147 (21-!) O NH; D0.

l s 03H EXAMPLE 148 1,000 pans of water which is 0-5 cold and the pH of the suspension is adjusted to 8.0 with dilute sodium hydroxide C P l (32H5 I solution. A solution of 26 parts of 2-ethylamino-4N} u NHFSOI 0 (S 031%): I chlorofonnyl-ethylammo 6 fluoro-s tnazme m 100 parts 0 F L W W/ acetone is poured into this suspension. Condensation is performed at 05 while stirring well and the hydrochloric acid liberated is neutralized by the addition dropwise of dilute sodium carbonate solution. On completion of the reaction, the

11111 11 new dyestuff is completely precipitated by the addition of sodium chloride, isolated in the presence of a buffering agent in this formula and dried in vacuo at 40. It corresponds to the formula given Pc represents the phthalocyanine structure. at h beginning f his example.

57.6 parts of copper phthalocyanine are heated for 3 hours if cotton is padded at 20 with a 2 percent solution of this at 145 in 270 parts of chlorosulfonic acid. The solution is yestuf which also c ntains 20 parts of Sodi m icar n e then cooled to 75 and 33.5 parts of thionyl chloride are added and 200 parts of urea per liter, and the impregnated goods are dropwise within 1 hour. The mixture is stirred for 3 hours at dried, then heated for 4 minutes at l30-l40 and finally 70-75, then cooled to room temperature and poured onto soaped at the boil for 30 minutes, then a pure turquoise blue 1,500 parts of ice. The suspension formed is filtered off and 5 5 dyeing is obtained which has very good wet and light fastness the precipitate is washed with 500 parts of 1 percent properties.

hydrochloric acid. The filter cake is then slurried in 500 parts Other amino-phthalocyanine dyestuffs are given in the folof water and 300 parts of ice, stirred with 15 parts of mlowing table 13, which are condensed asdescribed in example aminoacetanilide and the pH is adjusted to 7 by the addition of 148 with aqueous ammonia solution. The temperature is then slowly ala. 2-ethylamino-4-N-chloroformyl-ethylamino-6-fluoro-slowed to rise to 4050, the pH of the suspension always triazine,or with equivalent parts of being kept at 7.0-7.5 by the addition dropwise of ammonia b. Z-diethylamino-4-N-chloroformyl-methylamino-6-fluor0- solution. As soon as no more primary amine can be traced, s-triazine, 270 parts of 30 percent hydrochloric acid are added. The mixc. 2-methylamino-4-N-chloroformyl-methylamino-o-fiuoroture is heated for 3 hours at 85-90 and in this way the s-triazine, acetylamino group is saponified. d. 2-(4'-methylphenylthio)-4-N-chloroformyl- The amino-phthalocyanine dyestufi of the formula methylamino-6-fluoro-striazine,

e. 2-morpholino-4-N-chloroformyl-methylamino-tS-fluoros-triazine, or [CuPcT a f. 2-piperidino-4-N-chloroformyl-propylamino-6-fluoro-s- NH,-so,- (SO N9,)

L .1 The resulting reactive dyes have similar good properties as those of the preceding examples, and dyeings produced wherein PC has mean Elven above-ismobminedtherewith on cellulosic fibers, e.g., cotton, have the shades This dyestufl is then isolated by filtration, again slurried in given in the last column of table 13.

TABLE 13 Shade on Example cellulo se Number Ammo-phthalocyanine dyestufi fibres 149 a-f Turquoise S OzNH- S 03H blue. CuPc (SO2NH)3 NH,

S OZNHCHZCHRNIIi CuPc 151 a -i D0.

S QzNHCHzCHzNH; CuPc S O2NH2)3 EXAMPLE 152 s H (3H TH;

N @3N-N@ NHC ONl W-F H 0.. s J

l S 0 H 7 NH 7077113 23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in 400 parts of water, the pH being adjusted to 6.5 with sodium carbonate, and the solution is cooled to 0- 5". A solution of 24 parts of 2-methylamino-4-N-chloroformyl-methylamino-6-fluoro-s-triazine in 100 parts of acetate is added dropwise within minutes at this temperature and the pH of the reaction mixture is kept at 4.5-5.5 by the addition of sodium carbonate solution. As soon as no more unchanged amino compound can be traced, 30 parts of sodium bicarbonate are added to the solution and then a solution of 30.3 parts of diazotised Z-amino-naphthalene-l,S-disulfonic acid is poured in. On completion of the coupling, sodium chloride and buffer salts are added to the reaction mixture, the precipitated dyestuff is filtered off, washed with sodium chloride solution and stabilized with buffer salts. After drying in vacuo at 40, a red powder is obtained which dissolves in water with a red color. if mercerized cotton is padded with a 2 percent solution of this dyestuff at dried and then treated with a 1 percent sodium hydroxide solution which also contains percent sodium chloride, then steamed for 30 seconds c. 2-(4'-methoxyphenoxy)-4-N-chloroformyl-methylamino- G-fluoro-s-triazine, or

d. 2-(4'-chlorophenoxy)-4-N-chloroformyl-ethylamino6- fluoro-s-triazine, as described in example 152 and the condensation products are coupled as described in the same example, with the diazo components given in column ii. The shades of dyeings with the resulting reaction dyes on cellulose fibers are given in column IV of table l4.

18.8 parts of l,3-diaminobenzene-4-sulfonic acid are dissolved in 400 parts of water at a pH value of 4--4.5 and the solution is cooled to 05. Then within 15 minutes 27 parts of 2-dimethylamino-4-N-chloroformyl-methylamino-o-chloro-striazine dissolved in 100 parts of acetone together with an aqueous solution of sodium carbonate are dropped into this solution in such a manner that the pH value of the reaction mixture is maintained at 4-4.5. As soon as the reaction is completed, the reaction product is precipitated by addition of sodium chloride, filtered off, dissolved in 400 parts of water and diazotised at 0-5 with 25 parts of 30 percent hydrochloric acid and 6.9 parts of sodium nitrite. The resulting diazonium compound is coupled at a pH value of 4-5 with a solution of 48 parts of the condensation product of l 2'-sulfonic acid- 5'-aminophenyl)-3-methyl-5-pyrazolone and 2- dimethylamino-4-N-chloroformyl-methylamino-G-chloro-striazine (produced from the two components under the conditions described in example 152). After completion of the coupling. the new dyestufi is precipitated with sodium chloride, filtered oh" and washed with diluted sodium chloride solution. After drying in vacuo at 50, a yellow powder is obtained which dissolves in water with a yellow color.

if cotton or staple fiber is dyed with the new dyestuff according to the application methods described in the preceding 50 examples, a deep yellow dyeing of good fastness properties to at 100-l03, finally rinsed and soaped at the boil for 30 light and wet i obtained. s. t a red y s Obtamed which has y good Further dyestuffs with similar properties are obtained if the wet and tIaSmeSS w f diazo and coupling components listed in the followingtable 15 The table 14 hsts the mam moieties of other are reacted according to the conditions given in example 161 yf accorflll'lg the Invention having similar P p rties with (a) 2-dimethylamino-4-N-chloroformyl-methy[amino-6- whlcli y oblfimed y copdensms the coupling p nents chloro-s-triazine or equivalent parts of (b) 2-methylthio-4-N- comammg groups S column with chloroformyl-methylamino-6-chloro-s-triazine or (c) 2- y y ylamino-6-fluorodimethylamino-4-N-chloroformyl-methylamino-6-fluoro-ss-tnazl ne or equivalent parts of, triazine and are then diazotized and coupled as described in b. diethylammo-4-N-chloroformyl-methylamino-6-fluoro-sthe above example to form dyestuffs, the shade of which on cellulose fibers is given in the last column of the table 15.

TABLE 14 I II III IV Shade on cellulose Ex. No. Diazo component Acylatable coupling component fibres 153 (a to (1).... l-aminobenzene-2-sulphcnic acid l-arnino-s-hydroxynaphthalene-Zfidisulphonic acid Red. 154 (a to d).. Q-aminonaphthalene-l-sulphonic acid do Bluedish re (a to (1).... l-aminobenzene-Z-sulphonic acid l-amino-S-hydroxynaphthalene-4,6-disulphonic acid Red. 156 (a to d)..l. 2-eminonaphthalene-1,5-disulphonic acid do Bluiceish l'i. 57 (a to d).... l-amincbenzene-2,4-disulphonic acid 1-(4-aminophenyl)-3methyl-5-pyrazolone Yellow. 8 (a to d)...- l-amincbcnzene-2,5-disulphonic acid 2-amino-5-hydroxynaphthalene-7-sulphonic acid Orangev 159 (a to (1).... l-amincbenzene-Z-sulphonic acid Q-methylamino-5-hydroxynaphthalene-7-sulphonie acid... l D0. 4-aminoazobenzene-3,4-disulphonic acid ..do Scarlet.

i TABLE 15 Shade on cellulose Ex. No. Diazo component Coupling component fibres 162 (a to 1,3-diaminobenzene--sulphonic a'eid 1-amino-8-hydroxy-naphthalene-4,6-disulphonic acid Red. 163 (a to e). do 2 arnino-8-l1ydroxy-naphthalene-6-sulphonic acid. Red. 164 (a to c) 2-ethylamrno-S-hydroxy-naphthalene-(i-sulphonlc acid Red.

1-(4-aminophcnyl)-5-pyrazolone3carboxylic acid Yellow. ,do Do.

EXAMPLE 167 TABLE 16 I I[ Ill IV V C1 Shade on 3 N Ex. Aminoformazanc Acyloting cellulose l N N o. dyestufi Metal agent fibres C00 I 168 N-(2-hydiipxy-?- Cu 2-dirnplt1hylan1in01+ Blue.

aminop any -5- N-c oroformy HO3S sulphonic acid)- methyl-amino-fi- C N};-(2-lcarboiiychloro-s-ti'iazine.

p any -4 -su phonic acid)-ms-phenyl- N N formazano. 169 do On 2-dimethylamino-4- D0. N N N-chloroformylothyl-amino-fifluoro-s-tralzinc.

C 170 N(2-hydr0xy-3- Cu ..c,do Do.

nniinophcnyl-fisulphonic acid)-N- (2-l1ydr0xy-phonyl- 3',5'-disulphonic acid)-ms-phonyl formazanc. 171 do o o Cu 2-cthylthic-4-N- D0. chloro-[ormyl- 59.6 parts of copper complex compound of the amino- 3o ei a l ylamin -o c oro-sl'laZ 11c. forma'zane dyestufi of the formula 172 N-(Z-hydroxy-Zl- Cu 2-dimcthylamino-4- Do.

' N H; amlnophonyl 6- N-chloroiorrnyl- G O O 0 sulphonlc acid)- n1ethyl-aminc- N-(2-carb0xy ti-chloro-s- HO S- phenyl-4-sulphonic triazine.

Cu acid)-ms-o-sul- S phonic acid phenyl- O H orrnazane a 173 do Cu 2-dimothylamin0-4- Do.

I N-chloroiormyl- L i; methyl-aminc-G- fluoros-triazine. g 174. N-(Z-hydgpxy-Zi- Cu .d0 Do.

aminop any -5- sulphonlc acid) 1 N '-(2'-hydroxypheny1-3, 5-dlsulphonic ecld)-ms-osulphonic acid phenyl-ioi'mazane. 175 do Cu 2-dimcthylamino- D0. 4-N-chloroiormylr methyl-amino6 chloro-s-triazlnc.

176 d0 Cu Z-phcnylthiO--N- D (obtained by coupling diazotized 6-acetylam1no-2-am1no-lchlplrloiigmrygfi hydroxybenzene-4-sulfonic acid with the hydrazone from fifi g benzaldehyde and phenylhydrazine-Z-carboxylrc-acid-4-sulo ,fi... "of no fonic acid, reaction with a copper salt and saponification of EXAMPLE 177 the acetyl-amino group) are dissolved at a pH value of 6-6.5 in 600 parts of water. 33 parts of 2-phenoxy-4-N-chloroformyl-methyl-amindo-chloro-s-triazine dissolved in 80 parts of benzene together with an aqueous solution of sodium carone Hundred P are Introduced a q bonate are dropped into this solution within 1 hour at 2025 so that the reaction mixture remains neutral. As soon as no more starting material can be traced, the dyestuff is precipitated by addition of sodium chloride, filtered off, washed with diluted sodium chloride solution and dried cautiously in vacuo. It is a dark powder which, dissolved in warm water, gives a blue color.

The 2-phenoxy-4-N-chlor0formyl-methylamino-o-chloro-striazine mentioned in the preceding example is obtained by known methods by reacting 1 mol of cyanuric chloride in a first step with 1 mol methylamine and in a second step with 1 mol phenol and finally treating the condensation product with phosgene in toluene.

By using equivalent amounts of the metal-containing aminoformazane compounds shown in columns ll and III of the following table 16 and the acylating agents listed in column IV, and by maintaining the reaction conditions described in the preceding example 167, further dyestuffs according to the invention are obtained which have similar properties.

consisting of 4,000 parts of water of 40, two parts of the dyestuff according to example 1 five parts of 30 percent acetic acid and 0.5 part of a condensation product of stearyl amine and ethylene oxide. Within 20 minutes, the tempera- 50 ture of the dye bath is increased to boiling and maintained at the boil for 1 hour. After rinsing and drying, a brilliant yellow wool dyeing is obtained which has good wet and light fastness properties.

It has further been found, according to a second aspect of this invention, that another class of dyestuffs which can be fixed onto textile fibers containing hydroxyl and amino groups are produced by reacting dyestufis of the formula ,7 wherein D, n and R have the same meaning as in formula I, or D is the radical of a compound convertible into a dyestuff corresponding to D in Formula I, and

Hal and X have the same meanings as in formula II, n being preferably 1, and still more preferably compounds of the formula IX, with n mole of a tertiary basic compound which can be quatemized, which compound contains nitrogen, to form a dyestuff of the formula N W e1 31k yl (XIII) such production involving conventional azo coupling, condensation, and, where this is indicated, metallization.

In formulas III and X11, D represents, in particular, the radical of a technically easily accessible stable organic dyestuff, e.g., the radical of an optionally heavy metal-containing mono-, dis-, or polyaao dyestuff, of an anthraquinone, a nitro or a phthalocyanine dyestuff.

If D is the radical of an azo dyestuff then it is, e.g., the radical of a monoazo dyestufi' which may or may not contain heavy metal, from the benzene-azo-benzene, benzene-azonaphthalene, benzene-azo-pyrazole, benzene-azo-acylo-acetarylamide, naphthalene-azobenzene, napthalene-azonaphthalene and naphthalene azo-pyrazole series, or it is the radical of a disazo dyestuff from the benzene-azo-benzeneazo-benzene, benzene-azo-benzene-azo-naphthalene, bnezene-azo-naphthalene-azo-benzene, benzene-azunaphthalene-azo-naphthalene, and naphthalene-azo-benzneeazo-naphthalene series of the formazane series. If D is the radical of an anthraquinone dyestuff then it is preferably a lamino-4-phenylaminoor l-amino-4-diphenylaminoanthraquinone dyestufi radical.

If D is the radical of a nitro dyestufi' then it is e.g., the radical of a sulfonated nitrodiphenylamine. If D is the radical of a phthalocyanine dyestuff then it is preferably the radical of a phthalocyanine sulfonic acid alkyl or aryl amide, particularly a sulfonated one.

Preferred dyestuffs of formula Xll are those in which Am represents one of the groupings R beingmethyl, ethyl, or amino,

n being 1 or 2,

R representing alkyl of from one to 10 carbon atoms,

cyclohexyl or benzyl,

R representing hydrogen or lower alkyl and R, representing hydrogen, lower alkyl, or hydroxy-lower al- The dyestuffs mentioned can contain the substituents usual in dyestufis. Examples of such areLhalogen atoms such as fluorine, chlorine and bromine atoms, lower alkyl groups such as the methyl or ethyl group, lower alkoxy groups such as the methoxy or ethoxy group, carboxylic acid and sulfonic acid groups, acylamino groups such as the acetylamino, chloracetylamino or benzoylamino group, optionally N-substituted carboxylic and sulfonic acid amide groups, also the nitro, amino and hydroxyl group.

Advantageously, the dyestuffs contain two to five sulfonic acid groups.

An anion, e.g., a chlorine or bromine ion can serve to neutralize the quaternary ammonium group Am of formulas XII or XIII. If the dyestuff of formula XII contains acid saltforming groups, e.g., sulfonic acid groups, the quaternary ammonium group Am can also form an inner salt with the anion of one of these acid groups. The quaternized compounds may thus be represented generically by the following formula II I N (loworalkyl) D AX The quaternary ammonium group Am is preferably derived from quaternizable compounds, containing tertiary basic nitrogen, of the formula R; (X IV) In this formula R represents an optionally substituted aliphatic hydrocarbon radical, the H,N group or group wherein Z is hydrogen or an optionally substituted aliphatic hydrocarbon radical and Z is an optionally substituted aliphatic hydrocarbon radical, R, represents an optionally substituted aliphatic hydrocarbon radical and R, represents an optionally substituted aliphatic hydrocarbon radical and R, represents an optionally substituted aliphatic,

cycloaliphatic, or araliphatic hydrocarbon radical, or at least two of the symbols R,, R,, and R, together with the nitrogen atom, optionally with the inclusion of other hetero atoms such as oxygen or nitrogen, can form a mononuclear or 2... polynuclear heterocyclic ring.

As optionally substituted aliphatic hydrocarbon radicals in the positions of R,, R R and also of Z and Z, preferably alkyl radicals of at most tive, in the case of R of at most aliphatic carbon atoms can be used. These alkyl radicals can contain, as substituents, e.g.-, the hydroxyl group or low alkoxy groups such as the methoxy or ethoxy group. However, alkenyl radicals, especially the allyl radical, or alkinyl radicals such as the propinyl radical, can be aliphatic hydrocarbon radicals in the positions mentioned.

if R represents a cycloaliphatic hydrocarbon radical then this is, e.g., a 5 or 6-membered cycloalltyl radical, preferably the cyclohexyl radical. lf R is an araliphatic hydrocarbon radical then it is, e.g., an aor fl-arylalkyl radical, particularly the benzyl radical.

in a first preferred class of quaternisable compounds containing tertiary basic nitrogen of formula XIV:

a. R, and R: each represents a low alkyl radical, especially the methyl radical and R represents an optionally substituted aliphatic, cycloaliphatic or araliphatic hydrocarbon radical, or

b. at least two of the symbols R,, R and R together with the nitrogen atom, optionally with the inclusion of further hetero atoms, can form a mono or polynuclear heterocyclic ring.

Examples of case (a) are: trimethylamine, N,N-dimethyl-N- ethylamine, N,N-dimethyl-N-B-hydroxyethylamine, N,N- dimethyl-N-propylamine, N,N-dimethyl-N-butylamine, N,N- dimethyl-N-amylamine, N,N-dimethyl-N-allylamine, N,N- dimethyl-N-fi-ethoxyethylamine, N,N-dimethyl-l\l-cyclohexylamine or N,N-dimethyl-N-benzylamine.

Examples of case (b) are: acetaldchyde hydrazone, N- methyl-pyrrolidine, N-methyl-piperidine or N-methyl-1,2,3,4- tetrahydroquinoline or N-methyl-morpholine or N,N- dimethyl-piperazine. If all three R's take part in the ring formation, then the ring system consists, preferably, of two fused saturated rings wherein the nitrogen and one of R R and R, are components of both rings. Examples of this type of compounds are pyrrolizidine, quinuclidine, julolidine, lilolidine, hexahydrojulolidine, 1-azabicyclo-( 3,2,1 )-octane, l-azabicyclo-(3,3,l)-nonane, l,5-diazabicyclo-(3,3,l)-nonane and, preferably l,4-diazabicyclo-(2,2,2)-octane triethylenediamine).

in a second preferred class of quaternizable compounds containing tertiary basic nitrogen of formula XXV, R, represents an amino group, particularly the primary amino group, each of R and R represents a low alkyl radical or, together with the nitrogen atom, optionally with the inclusion of further hetero atoms, they can form a monoor polynuclear heterocyclic ring.

If each of R and R, together with the nitrogen atom, optionally with the inclusion of further hetero atoms, form a heterocyclic ring then this ring is, in particular, a pyrrolidine, piperidine, hexamethyleneimino, or morpholine ring. Examples of compounds of this type are N-amino-pyrrolidine, N- amino-piperidine, N-amino-hexamethyleneimine or N-aminomorpholine. I

in a third preferred class of quaternisable compounds containing tertiary basic nitrogen of formula XIV:

R represents a group wherein Z is hydrogen or a low alltyl radical and 2' represents a low alkyl radical, and

R, and R are each of low alkyl radical.

As low alkyl radicals for Z and 2', those containing one to four carbon atoms are preferred. R and R preferably represent the methyl group. Examples of such compounds are hydrazones from acetaldehyde, acetone, methylethyl ketone or diethyl ketone and hLNdimethyl-hydrazine.

A further preferred class of quaternizable compounds containing tertiary basic nitrogen are unsaturated-cyclic tertiary amines. These are preferably aromatic-heterocyclic amines,

. 3L e.g., quinoline, isoquinoline, or, particularly, pyridine, which can be substituted, e.g., by alkyl radicals and particularly by the methyl radical.

Examples of monovalent electron-donating substituent X are an alkoxy group such as the methoxy or ethoxy group; an aryloxy group, principally the unsubstituted phenoxy group, also however, a phenoxy group substituted by halogen, e.g., chlorine, low alkyl or alkoxy groups; a thioether group, i.e., an alkythio group such as the methylthio or ethylthio group, as well as an arylthio group, particularly the unsubstituted phenylthio group or the phenylthio group substituted by halogen, e.g., chlorine, low alkyl or alkoxy groups. Preferably however, X is a secondary or tertiary amino group, in particular a monoalkylamino or a dialkylamino group such as the methylamino, ethylamino, isopropylamino, t-butylamino, B- hydroxyethylamino group or the dimethylamino, diethylamino, dipropylarnino, dibutylamino or de-(B-hydroxethyl)-a.rnino group. X can also be derived from saturated heterocyclic nitrogen bases such as piperidine or morpholine; or X can be a cyclohexylamino group or a benzyl-amino, phenylamino or N-low alkyl-N-phenylamino group, the benzene nucleus of which can be substituted by halogen, eig, chlorine, low alkyl, or alkoxy groups.

The starting materials of formula Ill are obtained, for example, by condensing an organic dyestufif of formula l with n molecular proportion of a carbamic acid chloride of formula VI, as described under the first aspect of this invention.

Several of the quatemizable compounds according to the invention are known; all can be produced in a known way.

The reaction of the organic dyestuffs of formula Ill with the quaternizable compounds containing tertiary basic nitrogen is performed advantageously in a solvent at low temperatures, preferably at l0-60 C., the nitrogen compounds mentioned generally being used in excess. As solvent, principally water or a mixture of water with an inert organic solvent which is advantageously miscible with water such as acetone, methylethyl ketone, dioxan, or dimethyl formamide, is used. The end products are isolated and dried with care, for example by salting out with sodium chloride in neutral or weakly acid solution or by precipitating in an organic solvent such acetone, and by drying at a moderately raised temperature, preferably in vacuo.

Reactive dyestuffs of formula Xll are obtained by a modified process also by forming them from components of which at least one contains the radical of formula Xlll. This method is particularly suitable for the production of azo dyestuffs by coupling an aromatic diazonium compound with a coupling component of which at least one contains the reactive grouping of formula Xlll.

In a first method of performing this modified process, for example, the diazonium compound of an amine of the formula C (lower alkyl) Anionwherein Amfl R, X and A have the same meanings as given hereinbefore, A being particularly a radical of the benzene, diphenyl, naphthalene, benzene-azo-benzene, benzene-azonaphthalene or naphthalenc-azo-naphthalene series,

is coupled with a coupling component B-l-l wherein B represents the radical of a coupling component as defined in formula IV, particularly a radical of the hydroxybenzene, aminobenzene, hydroxyor amino-naphthalene, hydroxyor amino-pyrazole, or acyloacetylarylamide series, to form an az odyestuff of the formula N (lower alkyl) and optionally, dyestuffs of formula XVI possessing metallizable groupings of substituents, can be further reacted with agents yielding heavy metal, e.g., copper, nickel, chromium, or cobalt, to obtain the corresponding metal complex dyes.

regenerated cellulose fibers. By impregnating the textiles with aqueous dyestuff solutions or by printing them with thickened dyestuff solutions, drying the impregnated material and treating them with acid-binding agents, optionally while heating or Preferred anions Anion in formula XV and subsequent steaming, and after thorough rinsing and soaping, dyeings and formulas are chlorine or bromine. If A or B, infra, contains prints are obtained which are distinguished by excellent wet sulfonic acid groups, one of the latter may form an inner salt f tne ro erties and good fastness to light. What. has been with Am so that no outer anion is required to satisfy th P isaid with regard to dyeing techniques and fastness properties five charge of Am. of dyeings obtained with dyestuffs according to the first aspect In another method of Performing the mdified Process, the of this invention also applies in essence to the dyestuffs of the diazonium compound of an amine A--NH wherein A has the Second aspect h f, meaning given in formula is coupled with a coupling The dyestuffs according to this aspect of the invention are ponem ofihe nnul also suitable for the dyeing of hydroxyl groups containing fibers by the exhaustion process. For this purpose, during or N\ (ll w a y after dyeing, which is promoted, advantageously, by the addi- Animr tion of neutral salts such as sodium sulfate or chloride to the L I; I dyebath, the dyestufi is fixed by treatment with acid-binding agents.

As acid-binding agents, preferably sodium or potassium X (XVII) 2 bicarbonate, sodium or potassium carbonate, sodium metasilwherein i, B R and X have the meanings given icate, trisodium phosphate, sodium hydroxide solution and hereinbeforey to form a dyestufi of the formula also the sodium or potasslum salt of trichloroacetic acid are N (lower alkyl) used. In addition, thedye liquor or pnntmg paste can contain y other additives for example salts such as sodium sulfate or Anion F" chloride, or auxiliaries such as acid amides, e. g., urea, or addi- N N tives which prevent reduction such as nitrobenzene sulfonic acid.

| The reactive dyestuffs of formula XII are fixed with ad- A f X (XVIII) vantage at room temperature or at raised temperatures up to about 150C.

The dyestuffs of formula XII according to the invention are wherein fl and xhave h mean g g n herein: distinguished by very great reactivity and in addition they before; optionally dyestuffs of formula XVIII, thus obtained produce dyeings and prints having very good wet fastness prowhich possess metallizable groupings of substituenls, n b perties. Their reactivity is very much greater, usually at least reacted with agents giving ofl heavy metal, e.g., copper, 10 times and in some cases, even a hundred times greater, deniCkeL chromium. cobalt pendent on the nature of the substitution of the amino group Azo dyestuffs having two radicals of formula XIII are ob- A tha that of the starting materials of formula III, for tained,e.g., by coupling the diazonium compound of an amine which reason they can be fixed onto the fiber under conof formula XV with a coupling component of formula XVII. siderably milder conditions than the starting compounds.

In each case, the coupling is performed by the usual Also, compared with known dyestuffs containing the smethods in a weakly acid to weakly alkaline medium. triazine radical bound to the dyestuff by way of anamino Both the coupling as well as the metallization must be pergroup, the corresponding dyestuffs of formula XII according formed under mild conditions, i.e., high pH values and temto the invention have increased reactivity. peratures must be avoided. It is certainly unexpected that the urea bridge remains sta- The dyestuffs obtained can be stabilized by admixture with ble in the quaternization of the dyestuffs. Because, normally, buffer substances, e.g., with mixtures of primary and secondathe stability of the urea bridge is reduced on replacing the ry alkali phosphates or with alkali metal salts of sulfonated terelectron-donating substituent X by an electron-attracting subtiary aromatic amines, i.e., for example, with the sodium salt stituent, it was much more to be expected that the saponificaof N ,N-dimethylaniline-3-sulfonic acid. tion of the urea bridge would be very greatly facilitated by the Dyestuffs of formula XII which contain a water solubilizing introduction of the positive charge into the s-triazine ring. salt-forming group, preferably the sulfonic acid group, are The terms low" or lower" used in this specification and particularly suitable for the dyeing of natural and synthetic the appended claims in connection with an aliphatic radical polyamide fibers containing amino groups. In this case, aftermean that such radical has from one to five carbon atoms. treatment of the dyeing with acid-binding agents such as am- The following nonlimitative examples illustrate the invenmonia or hexamethylenetetramine causes an improvement of tion further. The temperatures are given therein in degrees the wet fastness. Centigrade. Everywhere, Q- represents an anion in ion rela- Water-soluble reactive dyestuffs according to the invention tionship to the ammonium group, e.g., a chlorine, bromine, or of fomiula XII containing two to five sulfonic acid groups are a sulfonate ion, which latter replaces one of the sulfonic acid used principally for the dyeing andprintingof textlle fibers groups shown in the formulas.

EXAMPLE 178 S03 CH3 CH3 CH3 i l //N N-1?I jN-oo-NH- N NH coo CH3 CH3 N l N N/ i (N9): (C a)2 69. 7 g. of tho dynstufl of the formula produced by condensation of the aininornonoazo dyestuff of the formula HnN- -N=NWC OOH S 03 ll with 2-chloro-4-dimethylamino-o-N-chloroformyl-N- methylamino-s-triazine, are dissolved in 1,000 ml. of water.

The pH of the solution is 7. At 2530, 12 g. of acetone-N,N- dimethyl-hydrazone are added to this solution whereupon the pH rises to about 9.4-9.6. As soon as no more starting materia] can be traced, the pH of the solution is adjusted to 6.5. The reaction product is precipitated by the addition of sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 60. The end product is a redyellow powder which dissolves in water with a yellow color. its constitution corresponds to the first formula given above.

If cotton is pad-dyed in a foulard with a 2 percent aqueous solution of this dyestuff which also contains 2 percent of sodium carbonate, the impregnated goods are stored for 4 hours at room temperature, then soaped at the boil and rinsed, a reddish yellow dyeing is obtained which has very good wet and light fastness properties.

if, instead of the 69.7 g. of the monoazo dyestufi' containing chloro-s-triazinyl groups used in this example, equivalent amounts of each of the azo dyestuffs containing chloroor bromo-s-triazinyl groups are used, which are obtained by condensation of an amino-azo dyestutf given in column ll of the following table 1 with the acylating agent given in column lll thereof, and each of these azo dyestuffs is reacted, respectively, with acetone-N,N-dimethyl-hydrazone, trimethylamine, N,N-dimethyl-N-ethylamine, N,N-dimethyl-N-B-hydroxyethylamine, N,N-dimethyl-N-allylamine, N,N-dimethyl-N- cyclohexylamine, N-methyl-pyrrolidine, N-methylmorpholine, N,N-dimethyl-hydrazine, N-aminopiperidine, N- amino-morpholine, pyridine, 3-methyl-pyridine or l,4-diazabicyclo-(2,2,2,)-octane, respectively, as described in the above example, then reactive dyestufis are obtained which produce light and wet fast dyeings on cellulose or polyamide fibers by the dyeing processes usual for these dyestuffs, e.g., that described in this example. The shade on cellulose fibers is given in column IV.

TABLE 17 I II III IV Shade on Example cellulose N0. Amlnoazo dyestufi Acylating agent fibres 179 2-aminonaphtha1ene-4,8-dlsulphonic acid I-aminO-E-mcthyIbcnZeno. 2-cl1tloro- 4-ethylamino-(l-N-chloroiormyl-N-clhylamino- Yellow.

sriazmc. 180 2-aminonaphthalene-5,7-disu1phonic acid-#aminohcnzcnc d0 D0. 181 2-aminonaphthalene-4,8-disulphonic acid-*1-amino 2-mcth0xy-5- do D0.

methylbenzenc. 182 4-a1ninoazobenzene-3,4-disulphonic acid 1-amino-3-methylbenzcne 2-bromo-4-dimethylamino-6-N-chlorol'ormyl-N- Orange.

mcthylamino-s-triazine. 183 1-amin0-3-acetylaminobcnzene-fi-sulphonic acid- 1-(2-chloro-5- 2cl1loro-4-dicthylamino-fi-N-chloroformyl-N-cthyl- Yellow.

sulphophenyl)-3-methyl-5-hydroxypyrazole, saponified. amino-s-triazinc. 184 1-amino-Ii-acctylaminobcnzene-G-sulphonic acid-M4, 8- do disulphonaphthyl-(2)l-3-nicthyl-fi-hydroxypyrazole, saponificd.

185 2-amino-4-nitrobnnzenc-l-sulphonic acid-1-benz0yalamino-8- 2-chloro-4-cthylaini1io-6-N-chloro[ormyl-N-cthylamino- Red.

hydroxynaphtllalenc-4,6-disulphonic acid, reduced. striazino. 186 2-amln0-4-nitrobnnzonc-l-sulphonic acid+1-benzoylamino-8- do Red.

hydroxynaphthalonc-Sfi-disulphonic acid, reduced. l87 2-amino-4-acctylaminobcnzonc-l-sulphonic ncid-1-hydroxy- 2-hromo-4-ctl1yla1nino-G-N-chloroformyl-Nethylodnaphthalene-4,fi-sidulphonic acid, saponificrl. amino-s-triazino. Orange 188 l-aminobenzone-2,5-disulphonic acid-vZ-amino-B-hydroxydo 011mg naphthalenc-7-sulplionic acid. 189 1-amino-2-hydroxy-3-acctylamlnohcnzcnc-fi-sulphonic acid- Z- 2-ln'omo-4-cthylamino-li-N-chlorolormyl-N-cthyl- Blur carboxy-fi-sulphobenzaldchydephenylhydi'azono copper complex, nmino-s-triazine. saponified. l-amino-Q-hydr0xy-3-acetylaminobenzene-5-sulphonic acid 2- do carboxy-E-sulphobenzaldehydc-4-sulphophenylhydmzono, copper complex, saponified. 191 I-aminobenzone2,5-disulphonic acid- 1-(4-aminobc1izoylamino)-8 2-chloro-4-cthylamii1o-6-N-chloroformyl-N-cthylamino- Red.

hydroxynaphthalcnc-Zi,(l-disulphonic acid. s-triazine. 2 2-amin0-4-acctylaminobnnzcne-l-sulphonic acid-+2-nn1inodo Orangenaphthalone-5,7-disulplionic acid, saponificd. 193 l-umlnobcnzene-2,fi-disulphonic acid-+1-(4 aminobunzoylmniiio)-8- in R hydtoxynaphthalone-4,6-dlsulph0nic acid. 194 Z-atnino-l-hydroxybonzcne-4,6-disulplionlc acid l-(3-nitrobolizoyl- (io w V101 amino)-8-hydi'oxynaphthalene-3,6-disulphonic acid, reduced, cop per complex. 195 2-amim-1-hydroxy-6-chlorobcnzenc i-sulphonic acid2-mnino-5- ...do Ruby hydroxyuaphthalcnc-7 sulphonic acid, copper complex. 196 2-amino-1-hydroxybcnznnc-i-sulphonic acid-+2-amino-8-hydroxy- 2-chloro-4-methylamino6-N-cl1loroformyl-N-methyl- Bordeaux.

naphthalene-G-sulphonic acid copper complex. umino-s-triazinu. 7 fi-nitro-l-cmino2-hydroxynaphthalcncA-sulphonic acid+2-umino-5- do 4 r Blackhydroxyuaphthalcnc-7-sulphonic acid, chromium complex 1; v 198 Z-amino+acotylamino+liydroxybcnzenc-fi-sulphonlc acid-+1- 2-chloro-4-mcthylamino-dN-cholroIormyl-N-mcthyl- Navy phenylamino-8hydroxynaphthalone-4,6-disulphonic acid, copper nmino s-triazinc b1110- complox, saponified. 199 2-amino-6-acctylamino-1-liydroxybonzonc-4-sulplionic acid 1- Z-brom0-4-cthylumino-fi-N-choloroformyl-N-cthyl- Ruby hydrogrgnlaphtliclciu-4,6-disulphonic acid, copper complex, mnino-s-triazino. sopom cr. 2 0 2-amino-6-acetylaminc-141ydroxybcnzenc-i-sulphonic acid-1-(2,5'- do 4 Yellow (lisulpihoghenyl)-3-methyl-5-hydroxypyrazolc, copper complex, sapon 1e 2-chloro-4-phenylamino-6-N-chloroformyl-N'nthyi- Yellow.

201 l-amino ii-acctylaminobcnzonc-G-sulphonic acid 1-(2,5-disulphophenyl)-3-methyl-B-hydroxypyrazole, saponiiied.

,, aminos-triazine. 

2. An azo dyestuff according to claim 1, wherein X is a dialkylamino radical, each alkyl moiety of said radical having up to four carbon atoms.
 3. An azo dyestuff according to claIm 1 of the formula
 4. An azo dyestuff according to claim 1 of the formula
 5. An azo dyestuff according to claim 1 of the formula
 6. An azo dyestuff according to claim 1 of the formula 